CN112670575A - Additive for lithium ion battery electrolyte and application thereof - Google Patents
Additive for lithium ion battery electrolyte and application thereof Download PDFInfo
- Publication number
- CN112670575A CN112670575A CN202011532076.0A CN202011532076A CN112670575A CN 112670575 A CN112670575 A CN 112670575A CN 202011532076 A CN202011532076 A CN 202011532076A CN 112670575 A CN112670575 A CN 112670575A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- additive
- ion battery
- lithium ion
- lithium
- 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
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 99
- 239000000654 additive Substances 0.000 title claims abstract description 79
- 230000000996 additive effect Effects 0.000 title claims abstract description 69
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 150000001540 azides Chemical class 0.000 claims abstract description 11
- -1 azide compound Chemical class 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 6
- SOUAUNWBTJIQRT-UHFFFAOYSA-N 2-azidoacetonitrile Chemical compound [N-]=[N+]=NCC#N SOUAUNWBTJIQRT-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229960002317 succinimide Drugs 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 2
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- KIQGRMGPIMCXSC-UHFFFAOYSA-N azidomethylsulfanylbenzene Chemical compound [N-]=[N+]=NCSC1=CC=CC=C1 KIQGRMGPIMCXSC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 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 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 5
- 239000002000 Electrolyte additive Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- WOEYOUBBHRYDLG-UHFFFAOYSA-N 2-azidoacetamide Chemical compound NC(=O)CN=[N+]=[N-] WOEYOUBBHRYDLG-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- GUWHRJQTTVADPB-UHFFFAOYSA-N lithium azide Chemical compound [Li+].[N-]=[N+]=[N-] GUWHRJQTTVADPB-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DIYVEJXQDMOGEL-UHFFFAOYSA-N 2-isothiocyanato-6-methylheptane Chemical compound CC(C)CCCC(C)N=C=S DIYVEJXQDMOGEL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229920006184 cellulose methylcellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- KLLQVNFCMHPYGL-UHFFFAOYSA-N 5h-oxathiole 2,2-dioxide Chemical compound O=S1(=O)OCC=C1 KLLQVNFCMHPYGL-UHFFFAOYSA-N 0.000 description 1
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101000892301 Phomopsis amygdali Geranylgeranyl diphosphate synthase Proteins 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YXXQUJVEYXWDSU-UHFFFAOYSA-N sulfo prop-2-enoate Chemical group OS(=O)(=O)OC(=O)C=C YXXQUJVEYXWDSU-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an additive for lithium ion battery electrolyte and application thereof, wherein the additive comprises an organic azide, the structural general formula of the organic azide is shown as a formula I, and the mass fraction of the additive is 0.1-5% based on 100% of the electrolyte. The organic azide can form a low-impedance interfacial film on the surfaces of the anode and the cathode of the battery as an additive, so that the quick charge and rate discharge performance of the battery can be effectively improved.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to an additive for a lithium ion battery electrolyte and application thereof.
Background
The power battery for the vehicle needs good quick charge performance and rate discharge performance, and higher energy density. In order to achieve better quick charge performance of the lithium battery, the conventional common technology is that a pole piece is made into a lower surface density or a lower compaction density in the manufacturing process of the battery, or more conductive agents are added into an electrode formula, so that lithium ions are better embedded and detached in the pole piece of the battery, but the energy density of the battery is reduced.
CN102683746A discloses an additive for electrolyte of lithium battery, and electrolyte and battery using the additive. The additive is an organic compound containing P or B elements, and is preferably a phosphate ester or borate compound. In the formation process of the battery, the additive can be decomposed under the action of an electric field to form two positive and negative groups with different charges. Wherein the positively charged groups move to the negative terminal to form a negative SEI film or are dissolved in the electrolyte, and the negatively charged groups move to the positive terminal and are deposited on the surface of the positive terminal to form a positive SEI film. The SEI film of the anode can effectively reduce the dissolution of Mn in the manganese anode material in the electrolyte, and increase the stability of the manganese anode material in the battery reaction, thereby prolonging the service life of the battery. The SEI film formed by the method has high strength but low elasticity, and cannot meet the quick charging performance of the current mainstream.
CN105609875B discloses an electrolyte additive and a high voltage electrolyte containing the electrolyte additive. The electrolyte additive is acrylic acid sulfuric anhydride derivatives. Adding 0.1-10% of additive into conventional electrolyte to prepare high-voltage electrolyte; the electrolyte has high oxidation potential (more than 4.5V), and can be matched with a high-voltage positive electrode material, which provides necessary conditions for obtaining a lithium ion battery with high energy density, and the addition of the additive is beneficial to forming a stable SEI film, so that the cycle performance of the battery can be prolonged. It is also not suitable for fast charging.
The batteries prepared by the electrolyte solution in the scheme have no quick charge performance, so that the development of the electrolyte solution for the lithium ion battery with high rate performance, good cycle performance and quick charge performance is necessary.
Disclosure of Invention
The invention aims to provide an additive for lithium ion battery electrolyte and application thereof. The organic azide is used as an additive of the lithium ion battery electrolyte, and can form a low-impedance interfacial film on the surfaces of the anode and the cathode of the battery, so that the quick charge and rate discharge performance of the battery can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an additive for lithium ion battery electrolyte, wherein the additive comprises an organic azide, and the structural general formula of the organic azide is shown as formula I:
wherein m and n are integers; and X is any one of amide group, carbonyl group, cyano group, sulfur atom, amino group or heterocyclic ring.
The organic azide compound is used as an additive of lithium ion battery electrolyte, and can form lithium azide (LiN) on the surface of an electrode through electrochemical reaction3) And finally form lithium nitride (Li)3N); since lithium nitride is a fast ion conductor and its ionic conductivity is orders of magnitude higher than some conventional inorganic lithium-containing compounds, such as Li3N ion conductivity up to 6 x 10 ═ s-3S cm-1While the ion conductivity of SEI film formed by conventional electrolyte can be as low as 10-31S cm-1For example, LiF ionic conductivity is σ 10-31S cm-1，Li2S ion conductivity σ of 10-13S cm-1，Li2CO3Ionic conductivity σ 10-8S cm-1Therefore, the organic azide is used as the additive of the lithium ion battery electrolyte, and the formed SEI layer has extremely high conductivity, so that the quick charge and rate discharge performance of the battery can be effectively improved.
According to the invention, acyl, ether and cyano modification is carried out on the azide compound, so that the additive has better solubility and wettability, the affinity performance to lithium ions is improved, an SEI film containing polymer components can be formed on the surface of an electrode through unsaturated CN groups and polyether groups, and the elasticity and strength of the SEI film are further improved.
The reaction equation is as follows:
X-N3→LiN3
LiN3+8Li++8e-→3Li3N。
preferably, m is an integer of 0 to 5, such as: 0.1, 2, 3, 4 or 5, etc., wherein n is an integer of 0 to 20, such as: 0.1, 3, 5, 10, 12, 15, or 20, etc.
Preferably, the organic azide compound includes: 2-azido acetamide
(as N)3-1), 2-azidoacetonitrile
(as N)3-2), 2-azido-1-benzodioxole-5-ethanone
(as N)3-3) azidomethylphenylsulfide
(as N)3-4), azido-PEG-acrylamide
(as N)3-5) and a succinimide monoester
(as N)3-6) or a combination of at least two thereof.
The organic azide compound can be obtained through a reagent purchasing platform commonly seen in the field, and the corresponding effect exerted when the organic azide compound is used as an additive for lithium ion battery electrolyte is almost irrelevant to the purchasing platform and is only relevant to the structure of the organic azide compound.
In a second aspect, the invention provides a lithium ion battery electrolyte, which contains the lithium ion battery electrolyte additive according to the first aspect, wherein the mass fraction of the additive is 0.1-5% based on 100% of the electrolyte, for example: 0.1%, 0.2%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, or 5%, etc.
Preferably, the electrolyte further includes a lithium salt.
Preferably, the lithium salt includes LiPF6Lithium bis (fluorosulfonylimide), LiFSI, lithium bis (trifluoromethanesulfonylimide), LiTFSI, and lithium tetrafluoroborate LiBF4Any one or a combination of at least two of lithium difluoroborate (LiODFB) and lithium difluorophosphate bis (LiODFP).
Preferably, the electrolyte further comprises a solvent.
Preferably, the solvent comprises propylene carbonate, ethylene carbonate and ethyl methyl carbonate.
Preferably, the mass fraction of the propylene carbonate is 3-8% based on 100% of the solvent, such as: 3%, 4%, 5%, 6%, 7%, 8%, etc.
Preferably, the mass fraction of the ethylene carbonate is 25-35%, for example: 25%, 27%, 28%, 30%, 32%, 24%, 35%, or the like.
Preferably, the mass fraction of the ethyl methyl carbonate is 60-70%, for example: 60%, 62%, 64%, 65%, 66%, 68%, 70%, or the like.
Preferably, the lithium ion battery electrolyte further comprises other additives.
Preferably, the other additives may further include vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, vinyl sulfate, 1-propene-1, 3-sultone, ethylene carbonate, tris (trimethylsilane) phosphite, lithium bis (fluorosulfonylimide), LiPO2F2And LiODFB, or a combination of at least two thereof.
In a third aspect, the present invention also provides a lithium ion battery, which comprises the lithium ion battery electrolyte according to the second aspect.
Preferably, the lithium ion battery further comprises a positive electrode plate, a negative electrode plate and a diaphragm.
Preferably, the positive electrode plate comprises a positive electrode material, carbon black, a conductive agent CNT, polyvinylidene fluoride and a positive electrode current collector.
Preferably, the positive electrode material includes any one or a combination of at least two of Ni83, lithium iron phosphate, NCM111, NCM442, NCM523, NCM622, NCM712, Ni75, NCM811, Ni88, Ni90, and Ni 95.
Preferably, the positive electrode current collector includes an aluminum foil.
Preferably, the negative electrode plate comprises a negative electrode material, carbon black, styrene butadiene rubber, carboxymethyl cellulose and a negative electrode current collector.
Preferably, the negative electrode material comprises any one of or a combination of at least two of a silicon carbon material, graphite or mesocarbon microbeads.
Preferably, the silicon carbon material comprises any one of carbon-coated silicon, carbon-coated silicon monoxide, a mixture of carbon and silicon or a mixture of silicon oxycarbide or a combination of at least two of the above.
Preferably, the negative electrode current collector includes a copper foil.
Preferably, the membrane is a ceramic membrane.
Compared with the prior art, the invention has the following beneficial effects:
(1) the electrolyte disclosed by the invention uses the organic azide compound as an additive, can improve the affinity of the additive and lithium ions, and can form compact lithium nitride (LiN) on the surface of an electrode3) The SEI film of the fast ion conductor, so that the fast charging performance of the battery can be greatly improved.
(2) The electrolyte can reduce the battery impedance, can obviously improve the quick charge performance and the rate discharge performance of the lithium battery on the premise of not reducing the energy density of the battery, and has the charging Direct Current Impedance (DCIR) below 43.6 and the discharging Direct Current Impedance (DCIR) below 46.5.
Drawings
Fig. 1 is a graph comparing the results of EIS tests of the batteries manufactured in example 3, example 5, example 10, example 13, example 18, and comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The organic azide compounds are purchased on a reagent purchasing platform: 2-azido acetamide
(as N)3-1, CAS: 1816-91-7), 2-azidoacetonitrile
(as N)3-2, CAS: 57707-64-9), 2-azido-1-benzodioxole-5-ethanone
(as N)3-3, CAS: 102831-07-2), azidomethyl phenyl sulfide
(as N)3-4, CAS: 77422-70-9), azido-PEG-acrylamide
(as N)35, available from common reagent purchasing platforms or reagent agencies such as the Goodpasture chemical network) and succinimide monoesters
(as N)36, common reagent purchase platforms or reagent agents such as those available from the Goodpasture chemical network).
Example 1
The embodiment provides a lithium ion battery, and the specific preparation method comprises the following steps:
(1) electrolyte preparation: in a glove box having a water content of less than 1ppm and an oxygen content of less than 2ppm, 50g PC, 300g EC and 650g EMC were mixed, and fully dried LiPF was added6So that the concentration of lithium salt in the electrolyte is 1.2mol/L, and the basic electrolyte is obtained. On the foundation0.2 percent of additive N is added into the electrolyte3-1, obtaining electrolyte E1.
(2) Manufacturing a battery: the positive electrode material Ni83, carbon black, conductive agent CNT, and PVDF were mixed in a ratio of 100: 0.7: 0.6: 1.5, coating on an aluminum foil with the thickness of 12 mu m, and drying at 85 ℃. Mixing carbon-coated silicon, carbon black, SBR and CMC in a ratio of 100: 0.9: 1.9: 1, and then the mixture is uniformly coated on a copper foil with the thickness of 8 mu m and is dried at the temperature of 90 ℃. The ceramic diaphragm is used as a diaphragm, and the positive and negative pole pieces are made into a battery C1 in a winding or lamination mode by a conventional method in the field.
(3) Formation aging grading process: the simulated cell was charged to 3.5V at 0.05C, then to 3.7V at 0.1C, then to 3.9V at 0.2C, and then aged at 45 ℃ for 48 h. After aging, the capacitor is fully charged at 0.33C and then discharged to 2.75V at 0.33C, which is the capacity grading.
Example 2
(1) Electrolyte preparation: in a glove box having a water content of less than 1ppm and an oxygen content of less than 2ppm, 60g PC, 320g EC and 620g EMC were mixed, and fully dried LiBF was added4So that the concentration of lithium salt in the electrolyte is 1.2mol/L, and the basic electrolyte is obtained. 0.4 percent of additive N is added into the basic electrolyte3-2, obtaining electrolyte E1.
(2) Manufacturing a battery: the positive electrode material NCM111, carbon black, conductive agent CNT, PVDF, and 100: 0.7: 0.6: 1.5, coating on an aluminum foil with the thickness of 12 mu m, and drying at 85 ℃. Mixing carbon-coated silica, carbon black, SBR and CMC in a ratio of 100: 0.9: 1.9: 1, and then the mixture is uniformly coated on a copper foil with the thickness of 8 mu m and is dried at the temperature of 90 ℃. The ceramic diaphragm is used as a diaphragm, and the positive and negative pole pieces are made into a battery C1 in a winding or lamination mode by a conventional method in the field.
(3) Formation aging grading process: the simulated cell was charged to 3.5V at 0.05C, then to 3.7V at 0.1C, then to 3.9V at 0.2C, and then aged at 45 ℃ for 48 h. After aging, the capacitor is fully charged at 0.33C and then discharged to 2.75V at 0.33C, which is the capacity grading.
Example 3
This example differs from example 1 only in that 0.2 is added to the electrolyte% additive N3-3, obtaining electrolyte E3, the cell obtained being C3.
Example 4
This example differs from example 1 only in that 0.2% of additive N is added to the electrolyte3-4, obtaining electrolyte E4, obtaining the cell C4.
Example 5
This example differs from example 1 only in that 0.3% of additive N is added to the electrolyte3-5, obtaining electrolyte E5, the cell obtained being C5.
Example 6
This example differs from example 1 only in that 0.3% of additive N is added to the electrolyte3-6, obtaining electrolyte E6, the cell obtained being C6.
Example 7
A nonaqueous electrolyte and a battery were prepared as described in example 1, except that the solvent composition was EC/EMC 30/70, the PC component was omitted, and 0.3% of additive N was added to the electrolyte3-1, obtaining electrolyte E7, the cell obtained being C7.
Example 8
This example differs from example 1 only in that 0.1% of additive N is added to the electrolyte31 and 0.1% of additive N3-5, obtaining electrolyte E8, the cell obtained being C8.
Example 9
This example differs from example 1 only in that 0.1% of additive N is added to the electrolyte3-2+ 0.1% of additive N3-5, obtaining electrolyte E9, the cell obtained being C9.
Example 10
This example differs from example 1 only in that 0.05% of additive N is added to the electrolyte3-3+ 0.15% of additive N3-5, obtaining electrolyte E10, the cell obtained being C10.
Example 11
This example differs from example 1 only in that 0.1% of additive N is added to the electrolyte34+ 0.2% of additive N3-5, obtaining electrolyte E11, the cell obtained being C11.
Example 12
This example differs from example 1 only in that 0.1% of additive N is added to the electrolyte3-1+ 0.2% of additive N3-6, obtaining electrolyte E12, the cell obtained being C12.
Example 13
This example differs from example 1 only in that 0.2% of additive N is added to the electrolyte3-2+ 0.1% of additive N3-6, obtaining electrolyte E13, the cell obtained being C13.
Example 14
This example differs from example 1 only in that 0.2% of additive N is added to the electrolyte3-3+ 0.1% of additive N3-6, obtaining electrolyte E14, the cell obtained being C14.
Example 15
This example differs from example 1 only in that 0.15% of additive N is added to the electrolyte34+ 0.15% of additive N3-6, obtaining electrolyte E15, the cell obtained being C15.
Example 16
This example differs from example 1 only in that the solvent composition EC/EMC is 30/70, 0.1% of additive N is added to the electrolyte3-1+ 0.1% of additive N3-5+ 1% LiFSI to obtain electrolyte E16, the cell obtained was C16.
Example 17
This example differs from example 1 only in that the solvent composition EC/EMC is 30/70, 0.1% of additive N is added to the electrolyte3-2+ 0.1% of additive N3-5+1％LiPOF2To obtain an electrolyte E17, and the obtained battery was C17.
Example 18
This example differs from example 1 only in that the solvent composition EC/EMC is 30/70, 0.05% of additive N is added to the electrolyte3-3+ 0.15% of additive N3-5+ 0.3% vinylene carbonate, giving electrolyte E18, giving a cell C18.
Example 19
This example differs from example 1 only in the solvent setForming EC/EMC 30/70, adding 0.1% additive N into electrolyte34+ 0.2% of additive N35+ 1% fluoroethylene carbonate, giving electrolyte E19, giving a cell of C19.
Example 20
This example differs from example 1 only in that the solvent composition EC/EMC is 30/70, 0.1% of additive N is added to the electrolyte3-1+ 0.2% of additive N36+ 1% of vinyl sulfate, giving electrolyte E20, the cell obtained being C20.
Comparative example 1
This comparative example differs from example 1 only in that no additives were added to the electrolyte to give an electrolyte DE1 and in that the cell obtained was DC 1.
Comparative example 2
This comparative example differs from example 1 only in that the solvent set EC/EMC is 30/70, no additives are added to the electrolyte, giving an electrolyte DE2, and the cell obtained is DC 2.
Comparative example 3
This comparative example differs from example 1 only in that 0.09% of additive N is added to the electrolyte3-1, obtaining an electrolyte DE3, the resulting cell being DC 3.
Comparative example 4
This comparative example differs from example 1 only in that 5.1% of additive N is added to the electrolyte3-1, obtaining an electrolyte DE4, the resulting cell being DC 4.
The compositions of the electrolytes described in examples 1 to 20 of the present invention and comparative examples 1 to 4 are shown in Table 1:
TABLE 1
And (3) performance testing:
1. DCIR test:
in examples 1 to 20 and comparative examples 1 to 4The cells after the formation, aging and grading are finished (5 in each condition, the results are averaged) are charged in a constant-current at 0.5C for 30min in a constant-temperature box at 25 +/-2 ℃, and are tested by an HPPC method, 2℃ is discharged for 10s, and the cells are kept stand for 40s, and 1.5C is actually charged for 10 s. The discharge DCR is calculated by the method of (V)0-V1) Current, the method of charging the DCR is charging DCR ═ V2-V3) 1.5C (current). Wherein V0Is 2C pre-discharge voltage, V1Is 2C post-discharge voltage, V2Is a 1.5C post-charge voltage, V3Is a 1.5C pre-charge voltage.
2. Step quick-charging test:
the batteries (5 in each condition, and the average value of the results) after the chemical composition capacity completion in examples 1 to 20 and comparative examples 1 to 4 were subjected to a quick charge test, wherein the quick charge step was 1.8C 10min, 1.6C 15min, 1.2C 4min, 1C 2min, 0.5C C constant current and constant voltage to 4.2V, and the cutoff current was 0.05C. The step of discharging is 1C constant current discharging to 2.75V. Fully charging and disassembling after 10 circles of circulation, and observing the lithium separation degree of the interface.
3. Symmetric battery testing
The batteries in examples 1 to 20 and comparative examples 1 to 4 (5 batteries under each condition, and the average value of the results is obtained) after the formation and capacity grading are completed are charged at a constant current of 0.5C and then charged at a constant voltage of 4.2V, the cut-off current is 0.05C, the discharge step is constant current discharge at 1C, the cut-off voltage is 2.75V, and after the cycle is completed for 100 times, the batteries are continuously charged at 0.5C for 30min and then disassembled. And respectively taking out the positive electrode and the negative electrode to prepare the button symmetrical battery with the positive electrode and the button symmetrical battery with the negative electrode and the negative electrode. EIS test is carried out on the symmetrical battery, the test equipment is Autolab PGSTAT302N, and the test frequency is 0.1-105HZ. And fitting the test result to obtain the Rct, namely the corresponding anode and cathode impedance. The impedances of the positive and negative electrodes were compared (100%). The impedance of other examples was converted into a ratio to a comparative example, and the EIS test results of the batteries manufactured in example 3, example 5, example 10, example 13, example 18, and comparative example 1 are shown in fig. 1.
The test results are shown in table 2 and fig. 1:
TABLE 2
As can be seen from table 2, it can be seen from the results of examples 1 to 20 and comparative examples 1 to 2 that the organic azide compound additive of the present invention can significantly improve the direct current resistance (DCIR) of the battery, thereby significantly improving the fast charging performance of the battery, specifically showing that no lithium precipitation occurs at the step fast charging interface, and further the test results of the symmetrical battery show that the additive of the present invention can simultaneously reduce the positive and negative resistances of the battery.
From the comparison of example 1 and example 4, the affinity of sulfur atoms for lithium is inferior to that of oxygen atoms, and the corresponding decrease in the resistance of the battery is deteriorated.
It can be seen from comparative examples 3 to 4 that the amount outside the range of the additive amount of the present invention is significantly deteriorated in the quick charge performance of the battery.
From examples 8-20, it can be seen that the organic azide additives of the present invention can be used in combination, and that short chain additives and long chain polyether azide additives can be used in combination to achieve better reduction of DCIR. The additive of the invention can be combined in different solvents and with some common additives such as LiFSI, LiPOF2VC, FEC, DTD, etc.
As can be seen from fig. 1, the organic azide compound of the present invention as an additive can significantly reduce the ac impedance of the battery.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The additive for the lithium ion battery electrolyte is characterized by comprising an organic azide, wherein the structural general formula of the organic azide is shown as a formula I:
wherein m and n are integers; and X is any one of amide group, carbonyl group, cyano group, sulfur atom, amino group or heterocyclic ring.
2. The additive for lithium ion battery electrolytes according to claim 1, wherein m is an integer of 0 to 5, and n is an integer of 0 to 20.
3. The additive for lithium ion battery electrolytes according to claim 1 or 2, wherein the organic azide compound comprises: 2-azido acetamide
2-Azidoacetonitrile
2-azido-1-benzodioxolane-5-ethanone
Azidomethyl phenyl sulfide
Azide-PEG-acrylamide
And a succinimide monoester
Any one or a combination of at least two of them.
4. A lithium ion battery electrolyte, characterized in that the electrolyte comprises the additive for lithium ion battery electrolytes according to any one of claims 1 to 3;
wherein the mass fraction of the additive is 0.1-5% based on 100% of the electrolyte.
5. The lithium ion battery electrolyte of claim 4 wherein the electrolyte further comprises a lithium salt;
preferably, the lithium salt includes LiPF6Any one or a combination of at least two of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium tetrafluoroborate, lithium difluorooxalate borate and lithium bis (oxalyldifluorophosphate).
6. The lithium ion battery electrolyte of claim 4 or 5 wherein the electrolyte further comprises a solvent;
preferably, the solvent comprises propylene carbonate, ethylene carbonate and ethyl methyl carbonate.
7. The lithium ion battery electrolyte of claim 6, wherein the mass fraction of the propylene carbonate is 3 to 8% based on 100% by mass of the solvent;
preferably, the mass fraction of the ethylene carbonate is 25-35%;
preferably, the mass fraction of the methyl ethyl carbonate is 60-80%.
8. The lithium ion battery electrolyte of any of claims 4-7, wherein the lithium ion battery electrolyte further comprises other additives.
9. The lithium ion battery electrolyte of claim 8 wherein the other additives comprise vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, vinyl sulfate, 1-propane, and mixtures thereofAlkene-1, 3-sultone, ethylene carbonate, tris (trimethylsilane) phosphite, lithium bis (fluorosulfonylimide), LiPO2F2Or a combination of at least two of the above.
10. A lithium ion battery comprising the lithium ion battery electrolyte of any one of claims 4-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011532076.0A CN112670575A (en) | 2020-12-22 | 2020-12-22 | Additive for lithium ion battery electrolyte and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011532076.0A CN112670575A (en) | 2020-12-22 | 2020-12-22 | Additive for lithium ion battery electrolyte and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112670575A true CN112670575A (en) | 2021-04-16 |
Family
ID=75407765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011532076.0A Pending CN112670575A (en) | 2020-12-22 | 2020-12-22 | Additive for lithium ion battery electrolyte and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112670575A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094175A (en) * | 2021-11-03 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Secondary battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020068222A1 (en) * | 2000-09-29 | 2002-06-06 | Kabushiki Kaisha Toshiba | Electric cell |
| CN102924495A (en) * | 2012-10-15 | 2013-02-13 | 中国科学院广州能源研究所 | Organic halogenosilane containing polyether chain and application of organic halogenosilane to non-aqueous lithium ion battery electrolyte |
| CN103688400A (en) * | 2011-04-27 | 2014-03-26 | 联邦科学与工业研究组织 | Lithium energy storage device |
| CN103715459A (en) * | 2013-12-24 | 2014-04-09 | 宁德新能源科技有限公司 | Lithium ion secondary battery and electrolyte thereof |
| CN105591158A (en) * | 2016-03-21 | 2016-05-18 | 东莞市杉杉电池材料有限公司 | Ternary cathode material lithium ion battery and electrolyte thereof |
| WO2019208153A1 (en) * | 2018-04-25 | 2019-10-31 | 株式会社Adeka | Nonaqueous electrolyte secondary battery |
| CN110752404A (en) * | 2018-07-23 | 2020-02-04 | 比亚迪股份有限公司 | Electrolyte, battery containing electrolyte and electric vehicle |
| CN111063932A (en) * | 2018-10-17 | 2020-04-24 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN111313093A (en) * | 2019-12-24 | 2020-06-19 | 安徽圣格能源科技有限公司 | Electrolyte and lithium battery |
| CN111313092A (en) * | 2020-03-04 | 2020-06-19 | 多氟多新能源科技有限公司 | Lithium ion battery electrolyte capable of improving film formation of positive electrode and negative electrode |
| CN111349026A (en) * | 2018-12-21 | 2020-06-30 | 石家庄圣泰化工有限公司 | Synthesis method of methoxy-bis (methylsulfonyl) azido ester |
-
2020
- 2020-12-22 CN CN202011532076.0A patent/CN112670575A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020068222A1 (en) * | 2000-09-29 | 2002-06-06 | Kabushiki Kaisha Toshiba | Electric cell |
| CN103688400A (en) * | 2011-04-27 | 2014-03-26 | 联邦科学与工业研究组织 | Lithium energy storage device |
| CN102924495A (en) * | 2012-10-15 | 2013-02-13 | 中国科学院广州能源研究所 | Organic halogenosilane containing polyether chain and application of organic halogenosilane to non-aqueous lithium ion battery electrolyte |
| CN103715459A (en) * | 2013-12-24 | 2014-04-09 | 宁德新能源科技有限公司 | Lithium ion secondary battery and electrolyte thereof |
| CN105591158A (en) * | 2016-03-21 | 2016-05-18 | 东莞市杉杉电池材料有限公司 | Ternary cathode material lithium ion battery and electrolyte thereof |
| WO2019208153A1 (en) * | 2018-04-25 | 2019-10-31 | 株式会社Adeka | Nonaqueous electrolyte secondary battery |
| CN110752404A (en) * | 2018-07-23 | 2020-02-04 | 比亚迪股份有限公司 | Electrolyte, battery containing electrolyte and electric vehicle |
| CN111063932A (en) * | 2018-10-17 | 2020-04-24 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN111349026A (en) * | 2018-12-21 | 2020-06-30 | 石家庄圣泰化工有限公司 | Synthesis method of methoxy-bis (methylsulfonyl) azido ester |
| CN111313093A (en) * | 2019-12-24 | 2020-06-19 | 安徽圣格能源科技有限公司 | Electrolyte and lithium battery |
| CN111313092A (en) * | 2020-03-04 | 2020-06-19 | 多氟多新能源科技有限公司 | Lithium ion battery electrolyte capable of improving film formation of positive electrode and negative electrode |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094175A (en) * | 2021-11-03 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111628218B (en) | Lithium ion battery and preparation method thereof | |
| CN111769329B (en) | Lithium ion battery | |
| CN107863556B (en) | Lithium ion battery with high nickel material as anode and silicon carbon material as cathode and electrolyte thereof | |
| CN110061292B (en) | Low-temperature electrolyte and lithium battery using same | |
| CN109309226A (en) | Electrochemical energy storage device | |
| CN109004275B (en) | Electrolyte solution and secondary battery | |
| CN111525192A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN111129590A (en) | High-voltage lithium ion battery non-aqueous electrolyte and high-voltage lithium ion battery | |
| CN112786964A (en) | High-voltage high-energy-density electrolyte and lithium battery thereof | |
| CN110911754B (en) | Lithium ion battery electrolyte and preparation method thereof | |
| CN116130766A (en) | Electrolyte and sodium ion battery | |
| CN113594547B (en) | Electrolyte and lithium ion battery | |
| CN114937813A (en) | Lithium ion battery and electronic device | |
| CN112670575A (en) | Additive for lithium ion battery electrolyte and application thereof | |
| CN110752404B (en) | Electrolyte, battery containing electrolyte and electric vehicle | |
| CN111430781A (en) | Ternary high-voltage lithium ion battery electrolyte and lithium ion battery thereof | |
| CN114605289B (en) | Carbamate compound for nonaqueous electrolyte and application thereof | |
| CN115332628A (en) | Lithium ion battery electrolyte, lithium ion battery and electric equipment | |
| CN115332626A (en) | Electrolyte and battery comprising same | |
| CN108767316A (en) | A kind of ternary material system lithium-ion battery electrolytes and lithium ion battery | |
| CN111864253B (en) | Lithium ion battery electrolyte and lithium ion battery | |
| CN112310475A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN114335729B (en) | High-voltage additive for lithium battery and electrolyte | |
| CN116979144A (en) | Electrolyte additive, electrolyte and lithium ion battery | |
| CN113328142A (en) | Electrolyte additive, electrolyte and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210416 |
|
| RJ01 | Rejection of invention patent application after publication |