CN110364695B - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN110364695B CN110364695B CN201810322643.6A CN201810322643A CN110364695B CN 110364695 B CN110364695 B CN 110364695B CN 201810322643 A CN201810322643 A CN 201810322643A CN 110364695 B CN110364695 B CN 110364695B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 105
- 239000003792 electrolyte Substances 0.000 claims abstract description 129
- -1 nitrile compound Chemical class 0.000 claims abstract description 53
- 239000007774 positive electrode material Substances 0.000 claims abstract description 36
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 29
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 27
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 23
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims description 27
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 13
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 230000006378 damage Effects 0.000 abstract description 13
- 239000010406 cathode material Substances 0.000 abstract description 7
- 238000002955 isolation Methods 0.000 abstract description 6
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 25
- 159000000002 lithium salts Chemical class 0.000 description 25
- 239000000463 material Substances 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 239000005416 organic matter Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- PGRMNXHYAZYNPG-UHFFFAOYSA-N fluoro hydrogen carbonate Chemical compound OC(=O)OF PGRMNXHYAZYNPG-UHFFFAOYSA-N 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 14
- 239000006258 conductive agent Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 239000011267 electrode slurry Substances 0.000 description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 238000007600 charging Methods 0.000 description 9
- 238000007086 side reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000007847 structural defect Effects 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000002733 (C1-C6) fluoroalkyl group Chemical group 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical group 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 230000002687 intercalation Effects 0.000 description 1
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- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a lithium ion battery, this lithium ion battery includes: a positive electrode including a positive electrode material including particles containing a lithium compound and an inorganic compound provided on surfaces of the particles; a negative electrode; an isolation film; an electrolyte comprising vinyl sulfate and a nitrile compound. The cathode material and the electrolyte are combined and cooperate, so that the damage of the cathode material structure and the oxidative decomposition of the electrolyte can be effectively inhibited under high voltage, and the cycle performance and the safety performance of the lithium ion battery under high voltage can be obviously improved.
Description
Technical Field
The application relates to the technical field of energy, in particular to a lithium ion battery.
Background
With the technical progress and market development in the fields of smart phones, unmanned planes and electric vehicles, the requirements of people on the performance of batteries are higher and higher. Lithium ion batteries have been the mainstream batteries used in such fields due to their advantages of high energy density, long cycle life, and no memory effect. At present, improving energy density and safety performance are two major research directions of high-performance lithium ion batteries. Increasing the operating voltage and using new high energy density materials are effective ways to increase the energy density of lithium ion batteries. Although new high energy density lithium ion battery materials have been a wide research focus, they are still in the basic research stage, and increasing the working voltage is still an important way to increase the energy density of the battery.
At present, the commercial lithium ion battery has a low working voltage, if the battery is under a high voltage, the oxidation activity of the anode material is increased, the structure is easily damaged, and the electrolyte is also easily decomposed under the high voltage, particularly, the electrochemical oxidation reaction is easily generated on the surface of the anode, so that the safety of the battery is reduced while the impedance of the anode is increased, the electrolyte is rapidly consumed, the battery expands, the battery cycle is deteriorated, and other performances are also reduced.
Thus, the current lithium ion batteries still need to be improved.
Disclosure of Invention
The present application is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present application is to provide a lithium ion battery with higher operating voltage, higher safety, better cycle performance, or higher energy density.
In one aspect of the present application, a lithium ion battery is provided. The lithium ion battery includes: a positive electrode including a positive electrode material including particles containing a lithium compound and an inorganic compound provided on surfaces of the particles; a negative electrode; an isolation film; an electrolyte comprising vinyl sulfate and a nitrile compound. The inventor finds that the cathode material and the electrolyte are combined and cooperate to effectively inhibit the damage of the cathode material structure and the oxidative decomposition of the electrolyte under high voltage, and can obviously improve the cycle performance and the safety performance of the lithium ion battery under high voltage, so that the lithium ion battery has higher working voltage or higher energy density, better safety performance and higher application value.
According to an embodiment of the present application, the electrolyte further includes a chain-type fluoro carbonate represented by formula 1,
wherein R is1Selected from alkyl with 1-6 carbon atoms or fluoroalkyl with 1-6 carbon atoms, R2Selected from C1-6 fluoroalkyl. The chain-shaped fluoro-carbonate has high flash point and good oxidation resistance, and the flash point and the oxidation resistance of the electrolyte can be improved by adding the chain-shaped fluoro-carbonate into the electrolyte, so that the cycle performance, the thermal stability and the safety performance of the lithium ion battery are improved.
According to embodiments herein, the chain fluoro carbonate is selected from one or more of the following organic compounds:
therefore, the chain-shaped fluoro-carbonic ester with the structure is added into the electrolyte, so that the effects of improving the flash point and the oxidation resistance of the electrolyte are better, and the cycle performance, the thermal stability and the safety performance of the lithium ion battery are higher.
According to the embodiment of the present application, the mass percentage of the chain-like fluoro carbonate is 5% to 40% based on the total mass of the electrolyte. Therefore, compared with other contents, the thermal stability of the electrolyte can be improved more remarkably by adding the chain-shaped fluoro carbonate with the mass fraction into the electrolyte, and the cycle performance and the safety performance of the lithium ion battery are further improved more remarkably.
According to an embodiment of the present application, the nitrile compound has a structural formula shown in formula 2:
wherein A is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 6 to 12 carbon atoms, and R3、R4Each independently selected from hydrogen atoms, cyano groups, nitrile groups or alkyl groups with 1-8 carbon atoms; x1、X2、X3Each independently selected from CH2O, CFH or CF2，n1、n2、n3Each independently selected from integers from 0 to 10. Therefore, the electrode of the lithium ion battery can be effectively protected, and the cycle performance of the lithium ion battery is improved.
According to embodiments of the present application, the nitrile compound is selected from one or more of the following organic compounds:
therefore, the nitrile compound can be adsorbed on the surface of the anode material in a tighter complexing mode, so that the structure of the anode material is not easy to damage, the electrolyte can be effectively isolated from the surface of the anode material, the interface between the electrode and the electrolyte is more stable, the oxidation of the anode of the lithium ion battery on the electrolyte in a charging state is reduced, and the cycle performance of the lithium ion battery is improved.
According to the embodiment of the present application, the mass percentage of the nitrile compound is 0.5% to 10% based on the total mass of the electrolyte. Therefore, compared with other contents, the addition of the nitrile compound with the mass fraction is more beneficial to forming a complex on the surface of the anode material, covering active sites, inhibiting the oxidation of the anode surface to the electrolyte, and has more obvious advantages under high voltage, so that the obtained lithium ion battery can work under high voltage and has higher energy density.
According to the embodiment of the application, the mass percentage of the vinyl sulfate is 0.5-3% based on the total mass of the electrolyte. Therefore, compared with other contents, the vinyl sulfate with the mass fraction can form a more stable interface film on the surface of the pole piece, can more effectively inhibit the occurrence of side reactions, can prevent the consumption of electrolyte and the loss of capacity in the circulating process, can obviously improve the circulating performance by adding the vinyl sulfate into the lithium ion battery, and can prolong the service life of the lithium ion battery.
According to an embodiment of the present application, the electrolyte further comprises one or more of fluoroethylene carbonate, vinylene carbonate, lithium bis (oxalato) borate. Therefore, fluoroethylene carbonate and vinylene carbonate have better film-forming property,
the lithium bis (oxalato) borate has better thermal stability due to the conjugated structure, and can participate in film formation of the anode and the cathode, so that the anode and the cathode can be protected from being damaged easily, the high-temperature performance of the lithium ion battery is improved, and the lithium ion battery is environment-friendly.
According to an embodiment of the present application, the electrolyte includes a lithium salt selected from one or more of inorganic lithium salts and organic lithium salts, the lithium salt being selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium difluorophosphate, lithium difluorosulfonimide and lithium bistrifluoromethanesulfonimide. Therefore, the lithium tetrafluoroborate is non-toxic and safe, the lithium hexafluoroarsenate has high electrical conductivity, the negative electrode has strong film-forming property, the lithium bis (trifluoromethanesulfonyl) imide has good thermal stability and high electrical conductivity, and the electrolyte has good stability and high safety property by adding one or more lithium salts into the electrolyte.
According to the embodiment of the present application, the concentration of the lithium salt is 0.5M to 1.5M, and according to the embodiment of the present application, the concentration of the lithium salt is 0.8M to 1.2M. Therefore, the lithium salt concentration in the range can ensure that the ion transference number of the electrolyte is higher, the conductivity is higher, the viscosity is more appropriate, and further the cycle performance and the rate capability of the lithium ion battery can be improved.
According to embodiments of the present application, the particles containing a lithium compound are selected from LiNix1Co1-x1O2、LiNix2MnyCo1-x2-yO2、LiCoO2Wherein 0.5. ltoreq. x1Less than or equal to 0.8 for LiNix2MnyCo1-x2-yO2，0≤x2≤0.8，0＜y≤0.3，0＜x2+y＜1。
According to an embodiment of the application, the inorganic compound comprises at least one element selected from the group consisting of: al, Mg, Zr, Ge, In, Ti, Zn. Therefore, the inorganic compound is coated on the surface of the particle containing the lithium compound, so that the active sites on the surface of the particle containing the lithium compound caused by the structural defects can be effectively covered, the side reaction between the surface of the particle containing the lithium compound and the electrolyte can be greatly reduced, the structural destruction of the particle containing the lithium compound can be simultaneously inhibited, the elution of the transition metal in the particle containing the lithium compound can be effectively prevented, and the safety risk caused by the deposition of the metal in the particle containing the lithium compound on the negative electrode can be reduced.
According to the embodiment of the application, the element in the inorganic compound accounts for 0.01-3% of the mass of the positive electrode material. Thus, the lithium ion battery can have higher safety performance and cycle performance by coating the inorganic compound on the surface of the particle containing the lithium compound than other contents.
Detailed Description
Embodiments of the present application are described in detail below. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The present application has been completed based on the following recognition and findings of the inventors:
under high voltage, the oxidability of the anode material of the lithium ion battery is enhanced, and particularly, the surface of the anode material is easy to generate side reaction with the electrolyte due to the existence of structural defects, so that the impedance of the anode is increased, the electrolyte is rapidly consumed, the performances of battery cycle and the like are deteriorated, and meanwhile, a series of safety problems are brought. The inventors have conducted intensive studies in view of the above-mentioned problems and, as a result of the studies, have found that the surface of a positive electrode material can be coated with a coating material, so that the active sites on the surface of the anode material caused by the structural defects are coated, thereby reducing the side reaction of the surface of the anode material and the electrolyte, meanwhile, the structure damage of the anode material is inhibited, the safety risk caused by the deposition of metal in the anode material on the cathode is reduced, meanwhile, in order to enable the lithium ion battery to stably work under high voltage, an additive with higher thermal stability can be added into the electrolyte, so that, under the combined action of the positive electrode material modified by the coating material and the electrolyte, compared with the positive electrode material modified by the coating material or the electrolyte not containing the additive, the cycle performance of the lithium ion battery under high voltage can be effectively improved, and the thermal stability and the safety performance of the lithium ion battery are improved.
In view of the above, in one aspect of the present application, a lithium ion battery is provided. The lithium ion battery includes: a positive electrode including a positive electrode material including particles containing a lithium compound and an inorganic compound disposed on surfaces of the particles; a negative electrode; an isolation film; an electrolyte comprising vinyl sulfate and a nitrile compound. The inventor finds that the lithium ion battery simultaneously adopts a coated anode material coated with an inorganic compound on the surface and an electrolyte with higher thermal stability, and the coated anode material and the electrolyte combine and cooperate to effectively inhibit the damage of the anode material structure and the oxidative decomposition of the electrolyte under high voltage, so that the cycle performance and the safety performance of the lithium ion battery under high voltage can be obviously improved. Specifically, the structure of the coated positive electrode material is not easy to damage, vinyl sulfate in the electrolyte can form a stable interface film on the surface of a pole piece, side reactions are inhibited, consumption of the electrolyte and loss of capacity in the circulation process are prevented, the circulation performance of the lithium ion battery can be improved, a nitrile compound can be adsorbed on the surface of the positive electrode material in a complexing mode, the structure of the positive electrode material is not easy to damage, the electrolyte can be effectively isolated from the surface of the positive electrode material, the interface between an electrode and the electrolyte is stable, and the positive electrode material and the electrolyte are combined for use, so that the lithium ion battery has high working voltage or high energy density, good safety performance and high application value.
According to an embodiment of the present application, the organic solvent includes a chain-type fluoro carbonate represented by formula 1,
wherein R is1Selected from alkyl with 1-6 carbon atoms or fluoroalkyl with 1-6 carbon atoms, R2Selected from C1-6 fluoroalkyl. Thereby, a chain-type fluorocarbonateThe flash point of the electrolyte is higher, the oxidation resistance is better, the flash point and the oxidation resistance of the electrolyte can be improved by adding the chain-shaped fluoro-carbonic ester into the electrolyte, and further the cycle performance, the thermal stability and the safety performance of the lithium ion battery are improved.
According to embodiments herein, the chain fluoro carbonate is selected from one or more of the following organic compounds:
therefore, the chain-shaped fluoro-carbonic ester with the structure is added into the electrolyte, so that the effects of improving the flash point and the oxidation resistance of the electrolyte are better, and the cycle performance, the thermal stability and the safety performance of the lithium ion battery are higher. According to some embodiments of the present application, the chain-like fluoro-carbonates have a lower number of fluorine atoms, and thus, fewer fluorine-containing by-products are generated during the recycling process, and the interfacial film is more stable.
According to the embodiment of the present application, in order to further improve the stability of the interface film, the chain-like fluoro carbonate may be 5% to 40% by mass based on the total mass of the electrolyte solution, and for example, the chain-like fluoro carbonate may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% by mass based on the total mass of the electrolyte solution. Compared with other contents, the effect of improving the stability of the interface membrane by adding the chain-shaped fluoro carbonate with the mass fraction into the electrolyte is better, the effect of improving the thermal stability of the electrolyte is better, and the cycle performance and the safety performance of the lithium ion battery are better. In some embodiments of the present application, the chain-type fluoro carbonate accounts for 10% to 30% by mass based on the total mass of the electrolyte, so that the stability of the interface film and the thermal stability of the electrolyte can be significantly improved, and the cycle performance and the safety performance of the lithium ion battery are better. When the mass percentage of the chain-shaped fluoro-carbonic ester is too high, the dissolution amount of the lithium salt is less, the capacity of the lithium ion battery is smaller, and further the cycle performance of the lithium ion battery is reduced compared with the cycle performance of the lithium ion battery when the mass percentage of the chain-shaped fluoro-carbonic ester is 5% -40%, but the cycle performance of the lithium ion battery is better than the cycle performance of the lithium ion battery which is not matched with the coated anode material; when the mass percentage of the chain-shaped fluoro-carbonic ester is too low, the thermal stability of the electrolyte is poor, so that the cycle performance of the lithium ion battery is reduced to a certain extent compared with the cycle performance of the lithium ion battery when the mass percentage of the chain-shaped fluoro-carbonic ester is 5-40%, the safety is low, and the cycle performance of the lithium ion battery is superior to the cycle performance of the lithium ion battery which is not matched with the coated cathode material.
According to an embodiment of the present application, the electrolyte includes a chain-type fluoro carbonate represented by formula 1 and one or more selected from the group consisting of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), γ -Butyrolactone (BL), Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), Ethyl Acetate (EA), and Tetrahydrofuran (THF).
According to the embodiment of the application, the lone pair electron energy level of the nitrile functional group in the nitrile compound in the additive is close to the energy level of the vacant orbit at the outermost layer of the transition metal atom in the lithium ion battery anode material, so that the organic molecule containing the nitrile functional group can be subjected to complex adsorption on the surface of the anode. The organic molecules adsorbed on the surface of the anode can well separate the easily-oxidized components in the electrolyte from the surface of the anode, so that the oxidation of the anode surface of the lithium ion battery in a charging state to the electrolyte is greatly reduced, and the cycle performance of the lithium ion battery is improved.
According to an embodiment of the present application, the nitrile compound has a structural formula shown in formula 2:
wherein A is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 6 to 12 carbon atoms, and R3、R4Each independently selected from hydrogen atoms, cyano groups, nitrile groups or alkyl groups with 1-8 carbon atoms; x1、X2、X3Each independently selected from CH2O, CFH or CF2，n1、n2、n3Each independently selected from integers from 0 to 10. Therefore, the electrode of the lithium ion battery can be effectively protected, and the cycle performance of the lithium ion battery is improved. According to embodiments of the present application, the nitrile compound is selected from one or more of the following organic compounds:
therefore, the nitrile compound can be more closely adsorbed on the surface of the anode material, so that the structure of the anode material is not easy to damage, the electrolyte can be more effectively isolated from the surface of the anode material, the interface of the electrode and the electrolyte is more stable, the oxidation of the anode of the lithium ion battery on the electrolyte in a charging state is reduced, and the cycle performance of the lithium ion battery is improved.
According to an embodiment of the present application, in order to further improve thermal stability of the lithium ion battery, the mass percentage of the nitrile compound is 0.5% to 10% based on the total mass of the electrolyte, for example, the mass percentage of the nitrile compound may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, etc., based on the total mass of the electrolyte. Therefore, compared with other contents, the addition of the nitrile compound with the mass fraction is more beneficial to forming a complex on the surface of the anode material, almost all active sites can be covered, the oxidation of the anode surface to the electrolyte is inhibited, the advantage under high voltage is more obvious, and the obtained lithium ion battery can work under high voltage and has higher energy density. When the mass percentage of the nitrile compound is lower, the nitrile compound is not enough to cover the active site on the surface of the anode material, and the oxidation effect of the anode surface on the electrolyte is inhibited to be poorer than that of the nitrile compound when the mass percentage of the nitrile compound is 0.5-10%, but the oxidation effect of the anode surface on the electrolyte is inhibited to be better than that of a lithium ion battery without combining the nitrile compound and the coating type anode material; when the mass percentage of the nitrile compound is high, free copper ions in the battery are deposited on the surface of the anode, so that the intercalation of lithium ions is inhibited, and the cycle performance of the battery is further deteriorated.
According to the examples herein, the structural formula of vinyl sulfate (DTD) is as follows:
and the mass percentage of the vinyl sulfate is 0.5 to 3% based on the total mass of the electrolyte, for example, the mass percentage of the vinyl sulfate may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, etc. based on the total mass of the electrolyte. Therefore, compared with other contents, the vinyl sulfate with the mass fraction can form a more stable interface film on the surface of the negative electrode, inhibit the occurrence of side reactions, prevent the consumption of electrolyte and the loss of capacity in the circulating process, remarkably improve the circulating performance and prolong the service life of the lithium ion battery by adding the vinyl sulfate into the lithium ion battery. When the content of the DTD is too low, an interface film is not favorably formed on the surface of the negative electrode, and the effect of inhibiting side reactions is not better than that of inhibiting the vinyl sulfate ester by 0.5 to 3 percent in mass percent, but is better than that of inhibiting the vinyl sulfate ester by not combining the vinyl sulfate ester with the coating type positive electrode material; when the content of DTD is too high, the film thickness formed on the surface of the negative electrode is too large to facilitate the passage of lithium ions, and the transfer resistance of lithium ions is increased, and the cycle capacity fading is accelerated.
According to an embodiment of the present application, in order to further improve thermal stability of the lithium ion battery, the electrolyte may further include one or more selected from fluoroethylene carbonate (FEC), Vinylene Carbonate (VC), and lithium bis (oxalato) borate (LiBOB). Therefore, the fluoroethylene carbonate and vinylene carbonate have good film-forming properties, so that the structure of the active material is not easy to damage, the lithium dioxalate borate has good thermal stability due to the conjugated structure, and the lithium dioxalate borate can participate in film formation of the anode and the cathode, so that the anode and the cathode are protected from being damaged, the high-temperature performance of the lithium ion battery is improved, and the lithium ion battery is environment-friendly.
According to an embodiment of the present application, the electrolyte includes a lithium salt selected from one or more of inorganic lithium salts and organic lithium salts. According to some embodiments of the present application, the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium perchlorate (LiClO)4) Lithium difluorophosphate (LiPO)2F2) Lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI). Thus, lithium tetrafluoroborate is non-toxic and safe; the lithium hexafluoroarsenate has high electrical conductivity and strong negative film-forming property; the lithium bis (trifluoromethanesulfonyl) imide has good thermal stability and high conductivity; the lithium hexafluorophosphate has good film forming performance, high conductivity, no toxicity, environmental friendliness and good comprehensive performance; one or more of the lithium salts are added into the electrolyte, so that the electrolyte has better stability, higher safety performance and better service performance. According to some specific examples of the present application, the lithium salt is selected from lithium hexafluorophosphate. Thus, the lithium salt has good comprehensive performance.
According to the embodiment of the present application, the concentration of the lithium salt is 0.5M to 1.5M, for example, the concentration of the lithium salt may be 0.5M, 0.6M, 0.7M, 0.8M, 0.9M, 1.0M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M, or the like. Therefore, the lithium salt concentration in the range can ensure that the ion transference number of the electrolyte is higher, the conductivity is higher, the viscosity is more appropriate, and further the cycle performance and the rate capability of the lithium ion battery can be improved. According to some embodiments of the present application, the concentration of the lithium salt is 0.8M to 1.2M. Therefore, the electrolyte has higher ion migration number, better viscosity and higher conductivity, so that the cycle performance and the rate capability of the lithium ion battery are better. When the concentration of the lithium salt is too low, the ion migration number is lower, and the conductivity is lower; when the concentration of the lithium salt is too high, the viscosity of the electrolyte is large, resulting in a decrease in the ion transfer rate and a decrease in the conductivity.
According to an embodiment of the present application, the particles containing a lithium compound in the positive electrode material are selected from LiNix1Co1-x1O2、LiNix2MnyCo1-x2-yO2、LiCoO2Wherein 0.5. ltoreq. x1≤0.8，0≤x2≤0.8，0＜y≤0.3，0＜x2+ y is less than 1; for LiNix2MnyCo1-x2-yO2, the ratio Ni/Mn/Co being selected from 1/1/1-8/1/1. According to an embodiment of the present application, the inorganic compound in the positive electrode material includes at least one selected from the following elements: al, Mg, Zr, Ge, In, Ti, Zn. The inorganic compound may cover the entire particle containing the lithium compound, or may cover a partial region of the surface of the particle containing the lithium compound. Therefore, the inorganic compound is coated on the surface of the particle containing the lithium compound, so that the active sites on the surface of the particle containing the lithium compound caused by the structural defects can be effectively coated, the side reaction between the surface of the positive electrode material and the electrolyte is greatly reduced, the structural damage of the positive electrode material can be inhibited, the dissolution of the metal in the positive electrode material is effectively prevented, and the safety risk caused by the deposition of the metal in the positive electrode material on the negative electrode is reduced.
According to the embodiment of the present application, in order to obtain a preferable effect, the content of the element in the inorganic compound in the positive electrode material is 0.01% to 3% by mass, and for example, the content of the element in the inorganic compound in the positive electrode material may be 0.01%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% by mass. Therefore, the inorganic compound is coated on the surface of the particle containing the lithium compound, so that the safety performance and the cycle performance of the lithium ion battery can be improved. According to some embodiments of the present application, the inorganic compound contains the element in an amount of 0.05 to 1% by mass based on the total mass of the positive electrode material. Therefore, the effect of improving the safety performance and the cycle performance of the lithium ion battery is better. When the mass percentage of the element contained in the inorganic compound is too low, the effect of improving the surface defect coverage of the anode is not obvious, and the structural stability of the anode material under high voltage is not obviously improved when being compared with that when the mass percentage of the element contained in the inorganic compound is 0.01-3 percent, but the effect is better than that when the particle which contains the lithium compound and is not coated by the inorganic compound is combined with the electrolyte; when the mass percentage of the element contained in the inorganic compound is too high, the capacity of the lithium ion battery is significantly reduced, and the cycle degradation is accelerated, but when the mass percentage of the element contained in the inorganic compound is too high, the performance is superior to that when the coating type positive electrode material is not used in combination with the electrolyte.
According to the embodiment of the application, the electrolyte and the positive electrode material are used in combination, specifically, the fluorinated chain carbonate, the nitrile compound and the vinyl sulfate can be used in combination and added into the electrolyte to form the electrolyte with high thermal stability, so that the stability of an electrode/electrolyte interface under high voltage can be effectively improved; meanwhile, the metal coating modified anode material is combined, so that the damage of the anode material structure under high voltage is inhibited, and the stability and safety of the battery under high voltage are comprehensively improved.
According to an embodiment of the present application, the positive electrode may include a binder and a conductive agent in addition to the positive electrode material described above. According to the embodiment of the present application, the materials of the binder and the conductive agent are not particularly limited, and those skilled in the art can flexibly select the materials according to actual needs as long as the requirements can be met. For example, the binder may be formed of styrene-butadiene rubber or polyvinylidene fluoride, and the conductive agent may be formed of conductive carbon black (super P). When in actual use, the positive electrode can be processed into a positive plate, specifically: preparing a positive electrode material, a conductive agent and a binder into positive electrode slurry in an N-methyl pyrrolidone (NMP) solvent; uniformly coating the positive electrode slurry on a current collector aluminum foil by 90% of the negative electrode capacity; drying, cold pressing and cutting into required shape. Therefore, the operation is simple and convenient, and the realization is easy.
According to the embodiment of the present application, the negative electrode includes a negative electrode active material, a binder, and a conductive agent, and the material of the negative electrode active material is not particularly limited as long as it can satisfy the requirement, and those skilled in the art can flexibly select the material according to the actual need. For example, the anode material may be graphite, amorphous carbon, nano silicon, nitride, or the like. According to the embodiment of the present application, the materials of the binder and the conductive agent are not particularly limited, and those skilled in the art can flexibly select the materials according to actual needs as long as the requirements can be met. For example, the binder may be formed of styrene-butadiene rubber or polyvinylidene fluoride, and the conductive agent may be formed of conductive carbon black. Therefore, the cathode material has high activity and good use performance. According to the embodiment of the application, in practical use, the negative electrode can be processed into the positive plate, specifically: uniformly mixing a negative electrode active material, a conductive agent, a thickening agent and an adhesive in deionized water to prepare negative electrode slurry; coating the negative electrode slurry on a current collector copper foil; drying, cold pressing and cutting into required shape.
According to the embodiment of the present application, the material and the type of the isolation film are not particularly limited, and those skilled in the art can flexibly select the isolation film according to actual needs as long as the requirements can be met. For example, the isolating membrane can be a microporous membrane, a composite membrane, a diaphragm paper, a rolled membrane and the like which are made of materials such as polyethylene, polypropylene and the like, so that the isolating membrane has excellent mechanical property and chemical stability, low price and good use performance. According to the embodiments of the present application, the thickness of the isolation film is not particularly limited, and those skilled in the art can flexibly select the thickness according to actual needs, which is not described herein in detail.
According to the embodiment of the application, the lithium ion battery further comprises a positive electrode current collector, a negative electrode current collector and other structures which the conventional lithium ion battery should have, and the materials of the positive electrode current collector and the negative electrode current collector are not particularly limited, and as long as the requirements can be met, a person skilled in the art can flexibly select the current collectors according to actual needs. For example, aluminum foil or the like may be used as the positive electrode collector, and copper foil or the like may be used as the negative electrode collector.
According to the embodiment of the application, in a general lithium ion battery, the thermal stability of the electrolyte is poor, the number of active sites exposed on the anode is large, so that the electrolyte is rapidly consumed, the anode impedance is large, the cycle performance is poor, and potential safety hazards exist. In the application, the inorganic compound is used in the positive electrode to modify the positive electrode material, and the nitrile compound and the electrolyte of the vinyl sulfate are used simultaneously, so that the stability of an electrode/electrolyte interface under high voltage can be effectively improved, the positive electrode material structure is inhibited from being damaged under high voltage, and the stability and the safety of the battery under high voltage are comprehensively improved.
Examples
The following description will be given taking as an example that the particles containing a lithium compound are lithium cobaltate, the inorganic compound containing element is Al or Zr, the chain-like fluorocarbonate is organic 6, organic 12, organic 15 or organic 30, and the nitrile compound is organic 31, organic 32, organic 33 or organic 34, and the following examples are given only for illustrating the present application and are not to be construed as limiting the present application. In the following examples and comparative examples, reagents, materials and instruments used were commercially available or synthetically available, unless otherwise specified.
Example 1
1. Preparation of positive plate
Stirring a positive electrode material, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) in an N-methyl pyrrolidone (NMP) solvent to prepare positive electrode slurry, wherein the particles containing a lithium compound in the positive electrode material are LiCoO2The inorganic compound contains Zr as an element, and the mass percentage of Zr is 0.5% based on the total mass of the cathode material. The solid content of the positive electrode slurry is 77 wt%, and the mass ratio of the positive electrode material, the conductive agent Super P and the PVDF in the solid component is 97.8:1: 1.2. Uniformly coating the positive electrode slurry on a current collector aluminum foil by 90% of the negative electrode capacity; drying at 85 ℃, and then carrying out cold pressing; then, after trimming, cutting into pieces and slitting, drying for 4h under the vacuum condition of 85 ℃ to prepare the lithium ion battery positive plate.
3. Preparation of negative plate
Graphite as a negative active material is uniformly mixed with a conductive agent Super P, a thickening agent sodium carboxymethyl cellulose (CMC) and a binding agent Styrene Butadiene Rubber (SBR) in deionized water to prepare negative slurry. In the negative electrode slurry, the solid content in the negative electrode slurry is 49 wt%, and the mass ratio of graphite, conductive agents Super P, CMC and SBR in the solid components is 97.7: 1: 0.3: 1. coating the negative electrode slurry on a current collector copper foil and drying at 85 ℃; and then, after trimming, cutting into pieces and slitting, drying for 12h under the vacuum condition of 120 ℃ to prepare the lithium ion battery negative plate.
4. Preparing an electrolyte:
the electrolyte was prepared in a dry argon atmosphere.
Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), Propyl Propionate (PP), and a mixture of Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), and Propyl Propionate (PP) in a mass ratio of EC: PC: DEC: PP: 15: 35: 20, adding 2% of organic matter 31 and 1% of DTD based on the total mass of the electrolyte, dissolving and uniformly mixing, and finally adding lithium salt lithium hexafluorophosphate (LiPF)6) And dissolving the electrolyte in the mixed solution, wherein the concentration of lithium salt is 1.15mol/L, and obtaining the electrolyte.
5. Preparing a lithium ion battery:
a6 μm polyethylene film (PE) was used as a separator. Stacking the prepared positive plate, the diaphragm and the negative plate in sequence to enable the isolating film to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; and (3) after welding a tab, placing the bare cell in an aluminum-plastic film outer package, injecting the prepared electrolyte into the dried lithium ion battery, packaging, standing, forming (charging to 3.3V at a constant current of 0.02C and then charging to 3.6V at a constant current of 0.1C), shaping, and testing capacity to finish the preparation of the lithium ion battery (the thickness of the soft package battery is 3.3mm, the width is 39mm, and the length is 96 mm).
Examples 2 to 6, 31 to 32
In line with the preparation of example 1, except that: the inorganic compound contains the kinds and contents of elements, and the kinds and contents thereof are varied as shown in Table 1.
Examples 7 to 10, 33 to 34
In line with the preparation of example 1, except that: the content of the organic material 31 was changed as shown in Table 1. Examples 11 to 13, 35 to 36
In line with the preparation of example 1, except that: the DTD content was varied, and the content was varied as shown in Table 1.
Examples 14 to 19
In line with the preparation of example 1, except that: the electrolyte solution also contained chain-type fluorocarbonic acid esters, and the kinds and contents of the chain-type fluorocarbonic acid esters were changed as shown in table 1.
Examples 20 to 22
In line with the preparation of example 1, except that: based on the total mass of the electrolyte, the electrolyte also contains 20% of organic matter 12, and organic matter 32, organic matter 34 or organic matter 33+ organic matter 34 replaces organic matter 31, and the type of the change is shown in table 1.
Example 23
In line with the preparation of example 1, except that: based on the total mass of the electrolyte, the electrolyte also contains 20% of organic matter 12, organic matter 33 replaces organic matter 31, and the content of DTD is 0.5%.
Example 24
In line with the preparation of example 1, except that: the electrolyte also contains 20% of organic matter 12 and 2% of FEC based on the total mass of the electrolyte.
Example 25
In line with the preparation of example 1, except that: the electrolyte also contains 20% of organic 12, 2% of FEC and organic 33 instead of organic 31 based on the total mass of the electrolyte.
Example 26
In line with the preparation of example 1, except that: the electrolyte also contains 20% of organic matter 12 and 2% of FEC based on the total mass of the electrolyte, and the content of DTD is 0.5%.
Example 27
In line with the preparation of example 1, except that: the electrolyte also contains 20% of organic matter 12 and 0.5% of VC based on the total mass of the electrolyte.
Example 28
In line with the preparation of example 1, except that: the electrolyte also contains 20% of organic matter 12 and 0.5% of LiBOB based on the total mass of the electrolyte.
Example 29
In line with the preparation of example 1, except that: the electrolyte also contains 20% of organic matter 12, 2% of FEC and 0.5% of VC based on the total mass of the electrolyte.
Example 30
In line with the preparation of example 1, except that: the electrolyte also contains 20% of organic matter 12, 2% of FEC, 0.5% of VC and 0.5% of LiBOB based on the total mass of the electrolyte.
Comparative example 1
In line with the preparation of example 1, except that: the positive electrode inorganic compound contains 0.5% of an element, and when an electrolyte is prepared, Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), Propyl Propionate (PP) are mixed at a mass ratio of EC: PC: DEC: PP of 10: 15: 35: 20, then mixed well and finally the lithium salt lithium hexafluorophosphate (LiPF)6) And dissolving the electrolyte in the mixed solution, wherein the concentration of lithium salt is 1.15mol/L, and obtaining the electrolyte.
Comparative example 2
In line with the preparation process of comparative example 1, except that: the electrolyte also contains 2% of organic matter 31 based on the total mass of the electrolyte.
Comparative example 3
In line with the preparation process of comparative example 1, except that: the electrolyte also contained 1% DTD based on the total electrolyte mass.
Comparative example 4
In line with the preparation process of comparative example 1, except that: the particles of the positive electrode containing lithium compounds have no inorganic compound on the surface, and the electrolyte also contains 2% of organic matter 31 and 1% of DTD based on the total mass of the electrolyte.
It is to be noted that the mass percentage of the solvent in each of the above examples and comparative examples means the mass percentage of each solvent calculated based on the total mass of the organic solvent, and the mass percentage of each additive means the mass percentage of each additive added based on the total mass of the electrolyte.
Table 1 shows the coating materials and contents, and the types and mass percentages of organic solvents and additives of the electrolyte
Table 2 comparative examples of coating materials and contents thereof and kinds and mass percentages of organic solvents and additives of electrolytes
The lithium ion batteries of examples 1 to 36 and comparative examples 1 to 4 were respectively tested for cycle performance and hot box performance (Hotbox), and the specific test method was as follows:
and (3) testing the cycle performance:
and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 20 minutes to keep the temperature of the lithium ion battery constant. Charging to 4.4V at 0.7C constant current, charging to 0.05C at constant voltage, and then discharging to 3.0V at 1C constant current, which is a charge-discharge cycle. And (3) repeatedly carrying out charge-discharge cycles with the capacity of the first discharge as 100% until the discharge capacity is attenuated to 80%, stopping testing, and recording the number of cycles as an index for evaluating the cycle performance of the lithium ion battery.
And meanwhile, the cycle performance of the lithium ion battery at 45 ℃ is tested, and the test method is the same as the test method for the cycle performance at 25 ℃.
Hotbox test:
and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 20 minutes to keep the temperature of the lithium ion battery constant. Discharging to 3V at constant current of 0.5C, standing for 5min, charging to 4.5V at constant current of 0.5C, and constant voltage charging to current of 0.05C to make the battery in 100% charging state. In a 25 ℃ incubator, left for 60 minutes, the Open Circuit Voltage (OCV), Impedance (IMP) before testing was recorded, appearance was checked and photographed. Heating to 150 + -2 deg.C at a rate of 5 deg.C/min + -2 deg.C/min, and maintaining for 60 min. And observing and recording the state of the sample in the testing process, and continuing to observe for 20min after the sample fails. After the test was completed, OCV, IMP were recorded, appearance was checked and photographed. If the lithium ion battery does not catch fire or explode, the lithium ion battery passes the test, otherwise, the lithium ion battery does not pass the test. And respectively testing 20 lithium ion batteries in each group, and recording the passing rate as: by number of cells/total number of cells.
The cycle performance and the results of the Hotbox test are shown in Table 3 for all examples and comparative examples.
TABLE 3
In table 3, comparing comparative example 4, examples 1 to 6, and examples 31 to 32, it is seen that the cycle performance is improved while the safety performance is improved when the positive electrode material is coated with Al or Zr, wherein Zr is superior in performance. The Zr coating amount is 0.01-3%. When the coating amount of Al or Zr is low, the defect sites of the positive electrode material cannot be effectively covered, and when the coating amount is high, the capacity of the positive electrode material is inhibited, and the cycle decay is fast.
Comparing comparative example 3, examples 7 to 10 and examples 33 to 34, it can be seen that the addition of the nitrile compound significantly improves the cycle performance of the battery, the content range is 0.5% to 10%, the addition of the nitrile compound is beneficial to forming a complex on the surface of the positive electrode material, covering active sites, and inhibiting the oxidation of the surface of the positive electrode on the electrolyte, and the advantage is more obvious particularly under high voltage. When the nitrile compound is small, it is insufficient to cover the active site on the surface of the positive electrode, and when the amount of the nitrile compound reaches a certain level, it will substantially completely complex the active site on the surface of the positive electrode.
Comparing comparative example 2, examples 11 to 13 and examples 35 to 36, it can be seen that the addition of DTD can also improve the cycle performance of the battery, with the content of 0.5% to 3%. The addition of DTD improves the cycle performance of the battery because DTD forms a stable interfacial film on the surface of the negative electrode to suppress the occurrence of side reactions, but when the content of DTD is high, the film is formed thick on the surface of the negative electrode to be unfavorable for the passage of lithium ions, so that the lithium ion transfer resistance is increased and the cycle capacity fading is accelerated.
Comparing comparative example 1 with examples 4 to 23, it can be seen that the battery cycle performance and safety performance can be improved simultaneously by adding an electrolyte of a nitrile compound, DTD and a fluoro solvent and combining the positive electrode surface coating technology.
Comparing example 1 with examples 14 to 19, it is clear that the addition of the chain-type fluoro carbonate can significantly improve the safety performance of the battery. When the content of the chain fluoro carbonate in the organic solvent is too low or too high, the cycle performance of the battery is reduced, and particularly, when the content of the chain fluoro carbonate is low, the advantage of thermal stability is not exerted, and when the content of the chain fluoro carbonate is high, the dissolution amount of the lithium salt is limited, and the capacity of the battery is also limited. The content of the chain-shaped fluoro carbonic ester is 5 to 40 percent.
Comparing example 14 with examples 24 to 30, it is clear that the cycle performance and safety performance of the battery can be further improved by fluoroethylene carbonate, vinylene carbonate and lithium dioxalate borate. The fluoroethylene carbonate and vinylene carbonate have good negative film-forming properties, so that a negative material is not easy to damage, the lithium dioxalate borate has good thermal stability due to the conjugated structure, and the lithium dioxalate borate participates in film forming of the positive electrode and the negative electrode, so that the positive electrode and the negative electrode can be protected from being damaged, the high-temperature performance of the lithium ion battery is improved, and the lithium ion battery is environment-friendly.
In the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present application, and that variations, modifications, substitutions and alterations may be made to the above embodiments by those of ordinary skill in the art within the scope of the present application.
Claims (5)
1. A lithium ion battery comprising:
a positive electrode including a positive electrode material including particles containing a lithium compound and an inorganic compound provided on surfaces of the particles;
an electrolyte including vinyl sulfate and a nitrile compound,
the inorganic compound contains Zr in an amount of Zr,
the mass percentage of the elements in the inorganic compound in the anode material is 0.01-1%,
the electrolyte also comprises chain fluoro-carbonic ester, and the chain fluoro-carbonic ester is selected from one or more of the following organic substances:
the nitrile compound is selected from one or more of the following organic compounds:
2. the lithium ion battery according to claim 1, wherein the mass percentage of the nitrile compound is 0.5 to 10% based on the total mass of the electrolyte.
3. The lithium ion battery according to claim 1, wherein the mass percentage of the vinyl sulfate is 0.5 to 3% based on the total mass of the electrolyte.
4. The lithium ion battery of claim 1, wherein the electrolyte further comprises one or more of fluoroethylene carbonate, vinylene carbonate, and lithium dioxalate borate.
5. The lithium ion battery of claim 1, said particles comprising a lithium compound being selected from LiNix1Co1-x1O2、LiNix2MnyCo1-x2-yO2、LiCoO2Wherein 0.5. ltoreq. x1≤0.8，0≤x2≤0.8，0＜y≤0.3，0＜x2+y＜1。
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