CN117613385A - Lithium ion battery electrolyte and lithium ion battery - Google Patents
Lithium ion battery electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN117613385A CN117613385A CN202311653275.0A CN202311653275A CN117613385A CN 117613385 A CN117613385 A CN 117613385A CN 202311653275 A CN202311653275 A CN 202311653275A CN 117613385 A CN117613385 A CN 117613385A
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- CN
- China
- Prior art keywords
- compound
- ion battery
- lithium ion
- lithium
- battery electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 72
- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 229940126062 Compound A Drugs 0.000 claims abstract description 17
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910052783 alkali metal Chemical group 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 239000006259 organic additive Substances 0.000 claims abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 16
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229940125898 compound 5 Drugs 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims description 2
- 229940126214 compound 3 Drugs 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000977 initiatory effect Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
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- 150000002431 hydrogen Chemical class 0.000 description 3
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
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- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
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- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
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- OSSBKXMASZTOSG-UHFFFAOYSA-N 2-(trifluoromethyl)oxolane Chemical compound FC(F)(F)C1CCCO1 OSSBKXMASZTOSG-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
Abstract
The invention provides lithium ion battery electrolyte and a lithium ion battery, wherein the electrolyte comprises electrolyte salt, organic solvent and additive, the additive comprises compound A and compound B, the structural formula of the compound A is shown as a structural formula I,wherein R is 1 、R 2 Each independently selected from one of hydrogen, alkyl, benzene ring, halogen, X represents hydrogen or alkali metal; the structural formula of the compound B is shown as a structural formula II,wherein,R 4 one selected from hydrogen, alkyl, benzene ring, halogen and fluoro hydrocarbon group, R 3 、R 5 Selected from silicon-containing groups. In the electrolyte of the invention, through the combined action of the compound A and the compound B, not only the surface of the electrode can be selectively modified and the decomposition of the cathode and the anode of the electrolyte after the formation can be reduced, but also H can be combined preferentially 2 O/HF is removed, so that the lithium ion battery has excellent initial effect, high-low temperature performance and cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to lithium ion battery electrolyte and a lithium ion battery.
Background
The energy density of the lithium ion battery may gradually increase as the active material changes. Currently, positive and negative electrodes of lithium ion batteries use high nickel content electrodes and graphite electrodes, respectively. However, the positive electrode interface stability of high nickel materials is the root cause of degradation of lithium ion batteries after full charge. In order to improve the interfacial stability of active materials, there are two conventional approaches: one is to coat or dope the surface of the positive electrode material, but this technique is not mature enough; the other is to add an additive which is easy to form a Solid Electrolyte Interface (SEI) into an organic electrolyte, and the method is in a continuous development stage, so great attention is paid to the method, but the research on the influence of a single additive in the electrolyte on a lithium ion battery is relatively large, and the research on the improvement of the lithium ion battery by combining two or more additives is relatively small.
Disclosure of Invention
The invention aims to provide lithium ion battery electrolyte which contains double additives and can effectively improve the performance of a lithium ion battery, in particular the high-low temperature performance and the cycle performance.
In order to achieve the above object, the present invention provides a lithium ion battery electrolyte comprising an electrolyte salt, an organic solvent, and an additive comprising a compound a and a compound B,
the structural formula of the compound A is shown as a structural formula I,
wherein R is 1 、R 2 Each independently selected from one of hydrogen, alkyl, benzene ring, halogen, X represents hydrogen or alkali metal;
the structural formula of the compound B is shown as a structural formula II,
wherein R is 4 One selected from hydrogen, alkyl, benzene ring, halogen and fluoro hydrocarbon group, R 3 、R 5 Selected from silicon-containing groups.
Compared with the prior art, the lithium ion battery electrolyte comprises electrolyte salt, an organic solvent and an additive, wherein the additive comprises a compound A and a compound B, the compound A contains an imidazole structure of a five-membered aromatic heterocyclic compound with two meta-position nitrogen atoms, an unshared electron pair of 1-position nitrogen atoms in the imidazole ring participates in annular conjugation, the electron density of the nitrogen atoms is reduced, hydrogen on the nitrogen atoms is easy to leave in a hydrogen ion form, the lithium ion battery electrolyte can be used for forming a polymer interface film on the surface of an electrode, fewer consumed electrons are generated, and the first effect is improved. During the initial formation stage, electrons accumulate at the surface of the negative electrode, and thus the imidazolyl cations migrate to the surface of the negative electrode (e.g., graphite). Meanwhile, the voltage of the positive electrode is increased, trifluoro anions migrate to the surface of the positive electrode material, and the additive can selectively modify the surface of the electrode, so that the decomposition of the cathode and the anode of the electrolyte after formation is reduced, and the cycle performance is improved. Compound B contains siliconGroups which form Si-O and Si-N and the effective functional group C=N in the amide group, can be combined with H preferentially 2 O/HF is removed, and the compound A is assisted to improve the cycle performance of the lithium ion battery together, so that the lithium ion battery has excellent initial effect, high-low temperature performance and cycle performance.
In some embodiments, R 1 、R 2 Each independently selected from one of hydrogen, alkyl, benzene ring, X represents hydrogen.
It will be appreciated that R 1 、R 2 May be the same or different, and is not limited herein.
In some embodiments, the alkyl is a substituted or unsubstituted C1-12 alkyl, i.e., an alkyl having 1-12 carbon atoms, which may be a chain alkyl or a cycloalkyl, and hydrogen on the ring of the cycloalkyl may be substituted with an alkyl. By way of example, alkyl groups can be, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, cyclohexyl, and the like.
In some embodiments, the benzene ring may be, but is not limited to, toluene, ethylbenzene, chlorobenzene, bromobenzene, nitrotoluene, aminotoluene, biphenyl, terphenyl, tetrabiphenyl, and the like.
In some embodiments, halogens include, but are not limited to, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the like.
In some embodiments, the alkali metal is selected from lithium or sodium.
In some embodiments, the fluorocarbon group may be linear, branched, or cyclic, and as an example, the fluorocarbon group may be, but is not limited to, a trifluoromethyl group, chlorodifluoromethane, dichlorotetrafluoroethane, dichloropentafluoroethane, and the like.
In some embodiments, R 4 Selected from alkyl or trifluoromethyl groups.
In some embodiments, the silicon-containing group is selected from at least one of a silane group, a siloxane group, a silicone group, and a silazane group. Preferably, the silicon-containing group is selected from a silane group, and as an example, the silicon-containing group is selected from a trimethylsilane group or a triethylsilane group, but not limited thereto.
It will be appreciated that R 3 、R 5 May be the same or different, and is not limited herein.
In some embodiments, the additive is present in the lithium ion battery electrolyte in an amount of 0.01 to 5% by mass, about 0.1 to 5% by mass, about 0.5 to 5% by mass, about 1 to 5% by mass, about 0.5 to 3% by mass, about 0.5 to 2% by mass, about 1 to 3% by mass, and about 1 to 2% by mass. By way of example, the mass percentages of the additives in the lithium ion battery electrolyte are 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some embodiments, the compound A is present in the lithium ion battery electrolyte in an amount of 0.1 to 5% by mass, about 0.5 to 5% by mass, about 1 to 5% by mass, about 0.5 to 3% by mass, about 0.5 to 2% by mass, about 1 to 3% by mass, and about 1 to 2% by mass. As an example, the mass percentage of the compound a in the lithium ion battery electrolyte is 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some embodiments, the mass percentage of the compound B in the lithium ion battery electrolyte is 0.1-5%, about 0.5-5%, about 1-5%, about 0.5-3%, about 0.5-2%, about 1-3%, about 1-2%. As an example, the mass percentage of the compound B in the lithium ion battery electrolyte is 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In some embodiments, the compound A is at least one selected from the group consisting of compound 1, compound 2, compound 3, compound 4, compound 5, and compound 6,
preferably, the compound A is at least one selected from the group consisting of a compound 1, a compound 4, a compound 5 and a compound 6, and the groups of the compounds have a surface active effect, so that the wetting capability of the electrolyte can be enhanced, the diffusion of the electrolyte can be accelerated, and the battery performance can be improved.
In some embodiments, the compound B is at least one selected from the group consisting of compound B1, compound B2, and compound B3,
in some embodiments, the electrolyte salt is selected from at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonimide, lithium bisoxalato borate, lithium difluorophosphate, lithium fluorosulfonate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium lower aliphatic carboxylate, lithium difluorobisoxalato phosphate, and lithium bisfluorosulfonyl imide.
In some embodiments, the lithium salt of the present invention is present in the electrolyte in a mass percent of 5 to 30%, about 5 to 25%, about 5 to 20%, about 5 to 15%, about 10 to 25%, about 10 to 20%.
In some embodiments, the organic solvent of the present invention is at least one of a carboxylate, carbonate, and ether compound. Among them, the carboxylic acid esters include cyclic carboxylic acid esters and chain carboxylic acid esters, and as examples, the cyclic carboxylic acid esters are γ -butyrolactone, γ -valerolactone, δ -valerolactone, and the chain carboxylic acid esters are Methyl Acetate (MA), ethyl Acetate (EA), ethyl Propionate (EP), butyl acetate (nba), propyl propionate (npp), butyl propionate. The carbonates include cyclic carbonates and chain carbonates, and specifically, the cyclic carbonates include Ethylene Carbonate (EC), propylene carbonate, butylene Carbonate (BC), pentylene carbonate, vinylene Carbonate (VC), or derivatives thereof; the chain carbonates include, but are not limited to, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), and Propylene Carbonate (PC). The ether compound includes cyclic ethers or chain ethers, for example, 1, 3-Dioxolane (DOL), 1, 4-Dioxane (DX), crown ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH 3-THF), 2-trifluoromethyl tetrahydrofuran (2-CF 3-THF) as cyclic ether; dimethoxymethane, diethoxymethane, ethoxymethoxymethane, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, diethylene glycol dimethyl ether are chain ethers, but are not limited thereto.
In some embodiments, the organic solvent of the present invention is present in the electrolyte in a mass percentage of 60 to 90%, about 64 to 90%, about 70 to 90%, about 80 to 90%, etc.
In some embodiments, the lithium ion battery electrolyte of the present invention may further include other additives, such as fluoroethylene carbonate (FEC), ethylene Sulfite (ES), dimethyl sulfoxide (DMSO), methyltrifluoroethyl carbonate (FEMC), ethylene carbonate (VC), ethylene carbonate (VEC), propylene Sulfite (PS), and the like, and the addition of other additives may improve battery performance.
Correspondingly, the invention also provides a lithium ion battery which comprises the anode material, the cathode material and the lithium ion battery electrolyte, and the lithium ion battery contains the lithium ion battery electrolyte, so that the lithium ion battery has excellent initial effect, high-low temperature performance and cycle performance.
In some embodiments, the positive electrode material may be, but is not limited to, nickel cobalt manganese oxide, as exemplified by a positive electrode material selected from LiNi x Co y Mn 1-x-y O 2 (0＜x＜1，0＜y＜1，x+y≤1)。
In some embodiments, the negative electrode material of the present invention is selected from at least one of artificial graphite, natural graphite, lithium titanate, silicon carbon composite material, and silicon oxide. As an example, the negative electrode material is artificial graphite, but is not limited thereto.
Detailed Description
For better illustrating the objects, technical solutions and advantageous effects of the present invention, the objects, technical solutions and advantageous effects of the present invention will be further illustrated by the following specific examples, but the present invention is not limited thereto, and the specific conditions may be performed according to the conventional conditions or the conditions suggested by the manufacturer, and the reagents or apparatuses used may be conventional products available commercially without the manufacturer's suggestion.
Example 1
(1) Preparation of electrolyte
In a glove box filled with argon (O) 2 ＜1ppm，H 2 O < 1 ppm), ethylene Carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the weight ratio of EC:EMC: DEC=1:1:1 to obtain 86.5g of organic solvent, then 0.5g of compound A (compound 1) and 0.5g of compound B (compound B1) are added, dissolved and fully stirred, then 12.5g of lithium hexafluorophosphate is added, and the electrolyte is obtained after uniform mixing.
(2) Preparation of the positive electrode
NCM811 (LiNi 0.83 Co 0.11 Mn 0.06 O 2 ) Uniformly mixing a conductive agent Super P and a binder PVDF according to a mass ratio of 95:4:1 to prepare lithium ion electrode anode slurry with certain viscosity, and coating the lithium ion electrode anode slurry on aluminum foil for a current collector, wherein the coating mass is 324g/m 2 And (3) drying at 85 ℃, cold pressing, trimming, cutting pieces, splitting, drying at 85 ℃ for 4 hours under vacuum condition, and welding the tab to prepare the lithium ion battery positive plate meeting the requirements.
(3) Preparation of negative electrode
Preparing artificial graphite material, thickener CMC and binder SBR (styrene butadiene rubber emulsion) into slurry according to the mass ratio of 97:1:2, coating the slurry on a current collector copper foil, and drying the slurry at 85 ℃ to obtain the coating with the coating weight of 168g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Trimming, cutting pieces, slitting, drying at 110 ℃ for 4 hours under vacuum condition after slitting, and welding tabs to prepare a lithium ion battery negative plate meeting the requirements;
(4) Preparation of lithium ion batteries
The positive plate, the negative plate and the diaphragm prepared according to the process are manufactured into a lithium ion battery with the thickness of 4.7mm, the width of 55mm and the length of 60mm through a lamination process, and the lithium ion battery is baked for 10 hours at the temperature of 75 ℃ in vacuum and injected with lithium ion battery electrolyte to prepare the lithium ion battery with the theoretical capacity of 1000 mAh.
The procedure for preparing electrolytes and preparing batteries in each example and each comparative example is the same as in example 1, and the components and contents are shown in table 1.
Table 1 electrolyte formulations for each example and each comparative example
The lithium ion batteries prepared in each example and comparative example were subjected to primary efficiency, normal temperature cycle, high temperature cycle performance and high temperature storage performance tests, respectively, and the test results thereof are shown in table 2.
First time efficiency test
And (3) under the condition of normal temperature 25 ℃, carrying out three-step constant current charging on the lithium ion battery after filling and standing for 24 hours: 1) Constant current 0.05C is charged for 1h, and constant current charging capacity C is recorded 1 The method comprises the steps of carrying out a first treatment on the surface of the 2) Constant current 0.1C charge for 1h, record constant current charge capacity C 2 The method comprises the steps of carrying out a first treatment on the surface of the 3) Constant current 0.2C charging for 4h, voltage limiting for 3.95V, recording constant current charging capacity C 3 Then the battery is sealed for the second time, and the battery after the secondary sealing is charged and discharged at the temperature of normal temperature (25 ℃) of 0.5C/0.5C, the upper and lower limit voltages are respectively 4.3V and 3.0V (the charge capacity is recorded as C) 4 The discharge capacity was designated C 0 ). Then discharging to 3.0V at 0.5C, repeating charging and discharging for 2 times, and finally charging the battery to 3.8V at 0.5C, and calculating the first charging and discharging efficiency of the lithium ion battery by using the following formula.
First charge and discharge efficiency= (C 1 +C 2 +C 3 +C 4 )/C 0 *100％
Normal temperature cycle test
The lithium ion battery is charged and discharged at the normal temperature (25 ℃) at 1.0C/1.0C (the discharge capacity is marked as C) 0 ) The upper limit voltage is 4.3V,then charging and discharging at 1.0C/1.0C for 500 weeks (discharge capacity is marked as C) 1 )。
Capacity retention= (C 1 /C 0 )*100％
High temperature cycle test
The lithium ion battery is charged and discharged at 1.0C/1.0C once under the condition of overhigh temperature (45 ℃) (the discharge capacity is marked as C) 0 ) The upper limit voltage was 4.3V, and then charging and discharging at 1.0C/1.0C was performed for 500 weeks under normal temperature conditions (the discharge capacity was noted as C) 1 )。
Capacity retention= (C 1 /C 0 )*100％
Low temperature discharge performance test
The lithium ion battery is charged and discharged at 0.5C/0.5C once under the condition of normal temperature (25 ℃) (the discharge capacity is marked as C) 0 ) The upper limit voltage was 4.3V, then the battery was charged to 4.3V under constant current and constant voltage conditions of 0.5C, the lithium ion battery was left in a low temperature tank of-20℃for 4 hours, and 0.5C discharge (discharge capacity was noted as C) was performed at-20 ℃ 1 ) The low temperature discharge rate of the lithium ion battery was calculated using the following formula.
Low temperature discharge rate = C 1 /C 0 *100％
High temperature storage test
Lithium ion batteries were charged and discharged at 0.3C/0.3C once (the discharge capacity of the battery was recorded as C) at normal temperature (25 ℃ C.) 0 ) The upper voltage limit is 4.50V; placing the battery in a 60 ℃ oven for 15d, taking out the battery, placing the battery in a 25 ℃ environment, discharging at 0.3C, and recording the discharge capacity as C 1 The method comprises the steps of carrying out a first treatment on the surface of the The lithium ion battery was then charged and discharged once at 0.3C/0.3C (the discharge capacity of the battery was recorded as C) 2 ) The capacity retention rate and the capacity recovery rate of the lithium ion battery were calculated using the following formulas.
Capacity retention= (C 1 /C 0 )*100％
Capacity recovery rate= (C 2 /C 0 )*100％
Table 2 lithium ion battery performance test results
As can be seen from the experimental results in table 2, the lithium ion batteries prepared in examples 1 to 8 were higher in initial efficiency, and were superior in normal temperature cycle performance, high temperature storage, high temperature cycle performance, and low temperature discharge performance to those of comparative examples 1 to 9. Because the additive of the invention comprises the compound A and the compound B, the imidazole structure of the five-membered aromatic heterocyclic compound containing two meta-position nitrogen atoms in the compound A, the unshared electron pair of the 1-position nitrogen atoms in the imidazole ring participates in the annular conjugation, the electron density of the nitrogen atoms is reduced, so that hydrogen on the nitrogen atoms is easy to leave in the form of hydrogen ions, the additive can be used for forming a polymer interface film on the surface of an electrode, and fewer electrons are consumed, thereby increasing the initial effect. During the initial formation stage, electrons accumulate at the surface of the negative electrode, and thus the imidazolyl cations migrate to the surface of the negative electrode (e.g., graphite). Meanwhile, the voltage of the positive electrode is increased, trifluoro anions migrate to the surface of the positive electrode material, and the additive can selectively modify the surface of the electrode, so that the decomposition of the cathode and the anode of the electrolyte after formation is reduced, and the cycle performance is improved. And a silicon-containing group of compound B, which can form effective functional groups C=N in Si-O and Si-N and amide groups, and can be combined with H preferentially 2 O/HF is removed, and the compound A is assisted to improve the cycle performance of the lithium ion battery together, so that the lithium ion battery has excellent initial effect, high-low temperature performance and cycle performance.
It is further known that the electrolytes of comparative examples 1 to 6 contained only compound a, did not contain compound B, and were weak in battery performance, and the electrolytes of comparative examples 7 to 9 contained only compound B, did not contain compound a, and were inferior in battery performance, and when the two were used in combination, they could act together, and the performance of the lithium ion battery was greatly improved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A lithium ion battery electrolyte comprises electrolyte salt, organic solvent and additive, wherein the additive comprises a compound A and a compound B,
the structural formula of the compound A is shown as a structural formula I,
wherein R is 1 、R 2 Each independently selected from one of hydrogen, alkyl, benzene ring, halogen, X represents hydrogen or alkali metal;
the structural formula of the compound B is shown as a structural formula II,
wherein R is 4 One selected from hydrogen, alkyl, benzene ring, halogen and fluoro hydrocarbon group, R 3 、R 5 Selected from silicon-containing groups.
2. The lithium ion battery electrolyte of claim 1, wherein the alkali metal is selected from lithium or sodium.
3. The lithium ion battery electrolyte of claim 1, wherein the silicon-containing group is selected from at least one of a silane group, a siloxane group, a silicone group, and a silazane group.
4. The lithium ion battery electrolyte according to claim 1, wherein the mass percentage of the compound a in the lithium ion battery electrolyte is 0.1-5%.
5. The lithium ion battery electrolyte according to claim 1, wherein the mass percentage of the compound B in the lithium ion battery electrolyte is 0.1-5%.
6. The lithium ion battery electrolyte according to claim 1, wherein the compound A is at least one selected from the group consisting of compound 1, compound 2, compound 3, compound 4, compound 5, and compound 6,
7. the lithium ion battery electrolyte according to claim 1, wherein the compound B is at least one selected from the group consisting of a compound B1, a compound B2, and a compound B3,
8. the lithium ion battery electrolyte of claim 1, wherein the electrolyte salt is selected from at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethane sulfonate, lithium bistrifluoromethylsulfonimide, lithium bisoxalato borate, lithium difluorophosphate, lithium fluorosulfonate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium lower aliphatic carboxylate, lithium difluorobisoxalato phosphate, and lithium bisfluorosulfonyl imide.
9. The lithium ion battery electrolyte according to claim 1, wherein the organic solvent is at least one of a carboxylate, a carbonate, and an ether compound.
10. A lithium ion battery, characterized by comprising a positive electrode material, a negative electrode material and the lithium ion battery electrolyte as claimed in any one of claims 1 to 9.
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