CN114421010A - Lithium-supplement type lithium ion battery electrolyte and application thereof - Google Patents
Lithium-supplement type lithium ion battery electrolyte and application thereof Download PDFInfo
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- CN114421010A CN114421010A CN202011176895.6A CN202011176895A CN114421010A CN 114421010 A CN114421010 A CN 114421010A CN 202011176895 A CN202011176895 A CN 202011176895A CN 114421010 A CN114421010 A CN 114421010A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 102
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- 239000013589 supplement Substances 0.000 title claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 58
- 230000000996 additive effect Effects 0.000 claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 27
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 23
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims abstract description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001323 Li2O2 Inorganic materials 0.000 claims abstract description 6
- 229910011140 Li2C2 Inorganic materials 0.000 claims abstract description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 5
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims abstract description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract 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 claims abstract description 5
- GUWHRJQTTVADPB-UHFFFAOYSA-N lithium azide Chemical group [Li+].[N-]=[N+]=[N-] GUWHRJQTTVADPB-UHFFFAOYSA-N 0.000 claims abstract description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims abstract description 4
- 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 abstract description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 22
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 20
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 18
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000011160 research Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 101100181929 Caenorhabditis elegans lin-3 gene Proteins 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a lithium-supplement type lithium ion battery electrolyte and application thereof, wherein the lithium-supplement type lithium ion battery electrolyte comprises: solvents, electrolytes and additives; the electrolyte may be at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, N-dialkylpyrrolidinium lithium salt, lithium difluorooxalato borate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium N-ethylpyrrolidinium tetrafluoroborate; the additive is selected from LiN3、Li2O2、Li2O、Li2C4O4、Li2C2O4、Li2C3O5、Li2C4O6And LixSyWherein x is not less than 1 and not more than 10，1≤y≤10。
Description
Technical Field
The invention relates to a lithium battery electrolyte, in particular to a lithium supplement type lithium ion battery electrolyte and application thereof, belonging to the technical field of lithium battery (lithium ion battery) electrolytes.
Background
The lithium ion battery is taken as a most advantageous high-energy chemical power supply, the research on the lithium ion battery is continuously and deeply developed in the world, active lithium released in the charging process of the current mainstream lithium ion battery in the first cycle compensates the first irreversible lithium loss and is used for forming an SEI film on the surface of a negative electrode so as to improve the reversible cycle capacity and cycle life of the lithium battery, the SEI film formed on the surface of the graphite negative electrode has 5-15% of first irreversible capacity loss, and the loss of a high-capacity silicon-based material is 15-35%. People research the prelithiation technology to improve the reversible cycle capacity of the lithium ion battery, and active lithium compensation is widely concerned.
The research on the components of the electrode material, whether the anode material, the cathode material or the separator is doped with lithium, is continuously carried out by the pre-lithiation technology. However, such research is usually complex and incomparable, the requirements for the environment are incomparable, and the high cost makes the real application very far, so the scenes of the real application are very few, and because the additive can generate great influence on the battery performance, some functional additives are added into the common electrolyte, so the lithium ion battery can adapt to different working environments, and the working performance is improved. Lithium battery electrolyte additives are of a wide variety, and almost every additive has one or more functions to improve the performance of a lithium battery. The research and development of the additives are the main content of the electrolyte research at present. However, the current requirements for electrolytes containing additives need to satisfy the requirement of good chemical stability, that is, the electrolyte itself, the electrolyte, electrode materials, separators, SEI films on the surfaces of electrodes, and the like do not chemically react when being laid aside or working.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a lithium electrolyte and an application thereof, so as to improve electrochemical properties of a battery, such as specific capacity, cycling stability, etc.
In one aspect, the present invention provides a lithium-supplement lithium ion battery electrolyte, including: solvents, electrolytes and additives; the electrolyte may be at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, N-dialkylpyrrolidinium lithium salt, lithium difluorooxalato borate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium N-ethylpyrrolidinium tetrafluoroborate; the additive is selected from LiN3、Li2O2、Li2O、Li2C4O4、Li2C2O4、Li2C3O5、Li2C4O6And LixSyWherein x is more than or equal to 1 and less than or equal to 10, and y is more than or equal to 1 and less than or equal to 10.
In the disclosure, the inventor firstly combines the development of the battery key materials and the identification of the process parameters such as the optimization of the anode and cathode interface films, and the like, and analyzes the materials together as an organic whole from local research to overall system research to finally obtain the high-performance lithium ion battery system with excellent performance. Specifically, the inventor of the present invention finds, through research, that a certain amount of unstable inorganic lithium salt is added to a lithium electrolyte as an additive, and the additive can supplement lithium element into an electrode material phase during charge and discharge, so as to solve irreversible lithium consumption, effectively increase reversible cycle capacity, and enable the reversible cycle capacity to exert the capacity of an electrode material to a greater extent more quickly. The capacity and the electrochemical stability of the battery cell are increased, so that the lithium battery can normally work in a harsher environment, the service life of the lithium battery can be prolonged, a higher electrochemical window can be provided, and the energy density and the power density are improved. The specific capacity gram capacity of the battery can be obviously improved, and the battery has higher coulombic efficiency of 98 percent and cycle stability: the capacity of 89% is kept after 600 cycles of circulation. The research result may provide certain basic data and theoretical basis for the industry enterprises in the aspects of improving the battery performance of the power battery, selecting materials, identifying process parameters and the like.
Preferably, the molar ratio of the electrolyte to the additive is 1: (0.001-0.2).
Preferably, the molar ratio of the electrolyte to the additive is 1: (0.005-0.2), preferably 1: (0.05-0.08).
Preferably, the solvent is an organic solvent, preferably at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl acetate, methyl acetate, methylethyl carbonate, glutaronitrile, and tetrahydrofuran.
Preferably, the concentration of the electrolyte is 0.0001-5M, preferably 0.5-5M.
Preferably, the concentration of the additive is 0.005-0.2M, preferably 0.05-0.08M.
Preferably, when the electrolyte concentration is 1M, the concentration of the additive is 0.005-0.2M, preferably 0.05-0.08M.
Preferably, the lithium-supplement type lithium ion battery electrolyte further comprises at least one of vinylene carbonate and fluorinated vinylene carbonate; the total volume of the vinylene carbonate and the fluorinated vinylene carbonate is 0.005-2% of the volume of the solvent.
In another aspect, the present invention further provides a lithium ion battery, including: the anode, the cathode and the lithium-supplement type lithium ion battery electrolyte.
Has the advantages that:
(1) the invention mainly researches that the electrolyte added with special additive can greatly improve the pre-lithiation treatment capability of the electrolyte, researches the influence of the pre-lithiation on the performance of the battery cell, and directly mixes the lithium supplement additive into the electrolyte of the lithium ion battery, thereby ensuring the production safety, and the whole process is simple and the cost is lower;
(2) in the invention, lithium is supplemented by electrolyte, and the electrolyte comprises: a lithium salt; an organic solvent; lithium supplement additives, including LixSy. The lithium supplement additive can also generate substances with high ionic conductivity and strong adhesion in the pre-charging process, so that the expansion of the negative electrode can be inhibited, and the cycle performance is improved;
(2) the electrolyte can obviously improve the specific capacity of the battery, and shows higher coulombic efficiency and cycling stability.
Drawings
FIG. 1 shows 1moL of lithium hexafluorophosphate (LiPF) used in example 16) Dissolving in 1L solvent (EC: EMC: DMC ═ 1:1:1+ 2% VC), and adding 0.02M LiN3Batteries made with the resulting electrolyte and with no LiN added3A comparative plot of different rate discharge capacities of the additive cells;
FIG. 2 shows 1moL of lithium hexafluorophosphate (LiPF) used in example 16) Dissolving in 1L solvent (EC: EMC: DMC ═ 1:1:1+ 2% VC), and adding 0.02M LiN3Batteries made with the resulting electrolyte and with no LiN added3Comparative plots of cycle life for different rates of discharge capacity of the additive cells.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, a lithium battery (lithium ion battery) electrolyte includes a solvent, an electrolyte, and an additive. The additive is unstable inorganic lithium salt, and can release lithium ions from the salt in the previous charging and discharging processes, so that lithium element is supplemented into an electrode material phase, irreversible lithium consumption is supplemented, and reversible cycle capacity can be effectively increased. Wherein the molar ratio of electrolyte to the additive may be 1: (0.001-0.2).
Hereinafter, the electrolyte solution for a lithium ion battery according to the present invention will be schematically described by taking an electrolyte solution for a lithium ion battery of one embodiment as an example.
The lithium ion battery electrolyte of the invention contains a solvent. As the solvent, an organic solvent such as Ethylene Carbonate (EC), Propylene Carbonate (PC), butylene carbonate, dimethyl carbonate (DMC), diethyl carbonate, ethyl acetate, methyl acetate, Ethyl Methyl Carbonate (EMC), glutaronitrile, tetrahydrofuran, or the like, which may be one or a combination of several of them, may be used. The solvent is preferably Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC) or diethyl carbonate, which is used in combination, due to the influence of conductivity and viscosity. In one example, EC is used: DMC 1:1 as solvent. Other additives described later may be added to the solvent. In another example, EC: EMC: DMC ═ 1:1:1+ 2% VC is used as the solvent.
In an alternative embodiment, the organic solvent has a water content of 5ppm or less. The capacity fading caused by the excessive moisture content is prevented.
The lithium ion battery electrolyte of the present invention contains a lithium salt as an electrolyte.
As the electrolyte, lithium hexafluorophosphate (LiPF) can be used6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate, lithium bis (oxalato) borate (LiBOB), lithium N-dialkylpyrrolidinium salt, lithium difluoro (oxalato) borate (LiODFB), lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium N-ethylpyrrolidinium tetrafluoroborate, and the like. These lithium salts may be used alone, or 2 or more kinds may be used in combination. The lithium salt is preferably lithium hexafluorophosphate (LiPF) due to the effects of solubility and conductivity6) Lithium tetrafluoroborate (LiBF)4)。
In an alternative embodiment, the concentration of the electrolyte in the lithium ion battery electrolyte of the present invention may be 0.0001 to 5M. The concentration of the electrolyte is preferably 0.5 to 5M due to the influence of viscosity and conductivity.
In alternative embodiments, the water content of the electrolyte may be less than or equal to 5 ppm. The capacity fading caused by the side reaction due to the excessive moisture content is prevented.
The lithium ion battery electrolyte of the invention contains an additive. As the above-mentioned additive, a special lithium salt, for example, selected from LiN, may be used3、Li2O2、Li2O、Li2C4O4、Li2C2O4、Li2C3O5、Li2C4O6And LixSyAnd the like.
In the present invention, the best matching additive concentration is selected in combination with the requirements for coulombic efficiency and capacity. In the lithium ion battery electrolyte, the concentration of the additive can be 0.005-0.2M. When the electrolyte is used in a lithium ion battery, the capacity of the lithium battery increases with the increase of the concentration of an additive added within a certain range (0.005-0.2M), and the coulombic efficiency is reduced after the capacity exceeds the range. Since the migration speed of lithium ions is influenced by viscosity, the concentration of the additive is preferably 0.05 to 0.08M.
With LiN3As an example, the inventor of the present invention finds, through research, that a certain amount of LiN3 is added to a lithium battery electrolyte as an additive, and the additive can effectively increase reversible capacity of a battery cell, increase conductivity and electrochemical stability of the electrolyte, so that not only can a lithium battery normally operate in a harsher environment, but also the service life of the lithium battery can be prolonged, and a higher electrochemical window can be provided, thereby improving energy density and power density. Thereby showing higher coulombic efficiency and cycle stability. Moreover, the addition of the additive into the electrolyte can accelerate the coordination adsorption of the positive and negative electrodes in the charging and discharging process, can remarkably increase the dissociation of the lithium ion solvent effect, and can be accompanied with the addition of the additive (such as LiN) within a certain range of content and power3) The concentration is increased, and the energy density of the lithium ion battery is effectively improved by the modified electrolyte.
The molar ratio of electrolyte to additive may be 1: (0.005-0.2), preferably 1: (0.0005 to 0.5), more preferably 1: (0.05-0.08). For example, when the electrolyte concentration in the electrolyte is 1M, the concentration of the additive is 0.005-0.2M, preferably 0.05-0.08M. The molar ratio of the electrolyte to the additive is 1: (0.005-0.2), the wettability is enhanced, and the advantages are complementary.
As an example, an additive LiN may be added to a general electrolyte (e.g., an EC: EMC: DMC ═ 1:1:1+ 2% VC electrolyte, etc.)3、Li2O2、Li2O、Li2C4O4、Li2C2O4、Li2C3O5、Li2C4O6And LixSyIn etc. ofAt least one of them.
In an alternative embodiment, the electrolyte may further include Vinylene Carbonate (VC), fluorinated vinylene carbonate (FEC), and other additives, so as to form a protective SEI film on the surface of the negative electrode. The volume usage amount of the other additives can be 0.005-0.2% of the volume of the solvent.
The electrolyte is used in the lithium ion battery, and can obviously improve the first effect: and shows higher coulombic efficiency of 98% and cycle stability: the capacity is kept 89% after 1000 cycles.
And (3) preparing the electrolyte. The preparation method comprises the following steps: the solute is injected into the mixed solution of the solvents, and the additives are added. The invention has simple process, easy control of the process and low preparation cost, and can be suitable for the field of electrolyte. Hereinafter, a method for producing the lithium ion battery electrolyte according to the present invention will be described as an example.
Firstly, weighing a certain amount of electrolyte, weighing an organic solvent (such as propylene carbonate) according to the required concentration, completely dissolving the electrolyte in the organic solvent, and uniformly stirring to obtain a clear transparent solution (mixed solution); and then, adding the additive into the mixed solution, and uniformly stirring to prepare the lithium battery electrolyte.
The electrolyte can be prepared in an oxygen-free, water-free and nitrogen-filled glove box, so that the conditions of abnormal failure of the battery and the like caused by high moisture and oxygen content in the air are reduced.
The lithium ion battery to which the electrolyte of the present invention is applied may include a positive electrode, a negative electrode, an electrolyte, and the like, and preferably may further include a separator. For example, the positive electrode may be lithium manganate, lithium nickelate, lithium iron phosphate, or the like. The negative electrode may be natural graphite, artificial graphite, hard carbon, or the like. The diaphragm can be a PP diaphragm, a PE diaphragm, an alumina fiber diaphragm and the like. Taking a lithium battery button cell as an example, a positive electrode material, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) are fully stirred and uniformly mixed in an N-methyl pyrrolidone solvent system according to a mass ratio of (85-90%) (5-10%), and then coated on a positive electrode current collector Al foil for drying to obtain a positive electrode plate, wherein the positive electrode material of the lithium ion battery may include lithium cobaltate, lithium manganate, lithium iron phosphate and the like; the lithium battery button cell can be obtained by taking a PE porous polymer film and the like as an isolating film, placing a diaphragm between a positive plate and a negative electrode (a graphite negative electrode material or a hard carbon negative electrode material prepared in the same way) and stacking the diaphragm in order, contacting the surface coated with an active material in the plate with the diaphragm, sealing the isolating film and the electrode plate by adopting a packaging shell, and filling the prepared electrolyte.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. In the following examples and comparative examples, the reagents, materials and instruments used were all commercially available as conventional reagents, conventional materials and conventional instruments unless otherwise specified, and the reagents involved therein were also synthesized by a conventional synthesis method.
Example 1
Preparing an electrolyte: 1moL of lithium hexafluorophosphate (LiPF)6) Dissolving in 1L solvent (EC: EMC: DMC ═ 1:1:1+ 2% VC), adding different concentrations (0.005M, 0.01M, 0.02M, 0.05M, 0.1M, 0.2M) of LiN3Then, fully stirring to prepare an electrolyte;
preparing a lithium battery button battery: dissolving polyvinylidene fluoride (PVDF) with the mass percent of 10% in N-2 methyl pyrrolidone (NMP), stirring until the polyvinylidene fluoride is completely dissolved, then pouring a positive electrode material (lithium cobaltate) with the mass percent of 80% and conductive acetylene black with the mass percent of 10% into the slurry, stirring at a high speed for 12 hours until the active material is completely dissolved, wherein the slurry is in a black colloid shape, uniformly coating 20 mu L of the slurry on a current collector, flatly placing the coated electrode plate in a drying box, baking for 5min at the temperature of 120 ℃ to completely volatilize the N-2 methyl pyrrolidone, placing a diaphragm between the electrode plate and the graphite negative electrode plate prepared by the same method, stacking the diaphragm in order, contacting the surface of the electrode plate coated with the active material with the diaphragm, sealing the isolating membrane and the electrode plate by using a packaging shell, and filling the prepared electrolyte, obtaining a lithium battery button cell;
and (3) testing electrical properties: the resulting cell was measured for capacitance, specific capacitance, energy density and power density using constant current on the Shanghai Chenghua CHI660D electrochemical workstation. The voltage test range is 3.0V to 4.2V.
Comparative example 1
In a common electrolyte (1 moL of lithium hexafluorophosphate (LiPF)6) The lithium battery was assembled in the same manner as in example 1 by dissolving 1L of a solvent (EC: EMC: DMC ═ 1:1:1+ 2% VC).
FIG. 1 shows 1moL of lithium hexafluorophosphate (LiPF) used in example 16) Dissolving in 1L solvent (EC: EMC: DMC ═ 1:1:1+ 2% VC), and adding 0.02M LiN3Batteries made with the resulting electrolyte and with no LiN added3Comparative plots of different rate discharge capacities of additive cells. As can be seen from fig. 1: the conventional electrolyte in comparative example 1 had a higher rate capacity than the electrolyte used in example 1 with 0.02M LiN added3The electrolyte of (1) has a low capacity, the 1C capacity difference is about 15mAh/g, the conventional electrolyte of comparative example 1 has a high rate of 5C capacity of 44mAh/g, and 0.02M LiN is added to the electrolyte of example 13The electrolyte of (3) has a higher capacity of 55 mAh/g.
FIG. 2 shows 1moL of lithium hexafluorophosphate (LiPF) used in example 16) Dissolving in 1L solvent (EC: EMC: DMC ═ 1:1:1+ 2% VC), and adding 0.02M LiN3Batteries made with the resulting electrolyte and with no LiN added3Cycle life of the additive cells is plotted. As can be seen from FIG. 2, the use of example 1 with 0.02M LiN addition3The electrolyte solution (2) had a more stable discharge capacity after 600 weeks, and the retention rate was 94%. The capacity retention rate of the conventional electrolyte is 90 percent after 600 weeks of circulation, and the capacity retention rate is obviously increased.
Example 2:
electrolyte solution: 1moL of lithium difluorooxalato borate (LiODFB) was dissolved in 1L (EC:DMC 1:1:1+ 2% VC, and Li (0M, 0.005M, 0.01M, 0.02M, 0.05M, 0.1M, 0.2M) was added thereto at different concentrations2O2Then, the mixture was sufficiently stirred to prepare an electrolyte. The cell was prepared as in example 1. The electrical properties were tested as in example 1.
Example 3:
electrolyte solution: 1moL of lithium hexafluorophosphate (LiPF)6) Dissolving in 1L (EC: EMC: DMC ═ 1:1:1+ 2% VC), adding 0.1M and Li at different concentrations (0M, 0.005M, 0.01M, 0.02M, 0.05M, 0.2M, respectively)2C4O4Then, the mixture was sufficiently stirred to prepare an electrolyte. The cell was prepared as in example 1. The electrical properties were tested as in example 1.
Example 4:
electrolyte solution: 1moL of lithium bis (fluorosulfonyl) imide (LiFSI) was dissolved in 1L of solvent (EC: DMC 1:1), and 0.01M and Li at different concentrations (0M, 0.005M, 0.02M, 0.05M, 0.1M, 0.2M, respectively) were added2C3O5Then, the mixture was added and sufficiently stirred to prepare an electrolyte. The cell was prepared as in example 1. The electrical properties were tested as in example 1.
Example 5:
electrolyte solution: 1.5moL of lithium N-ethylpyrrolidinium tetrafluoroborate was dissolved in 1L of a solvent (EC: DMC 1:1), and 0.2M and Li at different concentrations (0M, 0.005M, 0.01M, 0.02M, 0.05M, 0.1M, respectively) were added2C4O6Then, the mixture was sufficiently stirred to prepare an electrolyte. The cell was prepared as in example 1. The electrical properties were tested as in example 1.
Example 6:
electrolyte solution: 1moL of lithium hexafluorophosphate (LiPF)6) Dissolved in 1L of a solvent (EC: EMC: DMC ═ 1:1:1+ 2% VC), and then Li was added at a concentration of 0.05MxSy(x ═ 2, y ═ 3), and then, the mixture was sufficiently stirred to prepare an electrolyte solution.
Table 1 shows the compositions of the electrolytes prepared in examples 1 to 5 of the present invention and the performance parameters obtained by the tests:
it can be seen from table 1 that the addition of the additive can improve the first-pass retention of the battery, and the addition of the additive can reduce the irreversible lithium consumption loss to the battery capacity, and mainly replenishes the lithium element. But the corresponding contents are substantially different for different additives while simultaneously improving the cycle performance: for example, the additive is LiN3When the concentration is 0.005-0.01M, the first-effect retention rate can be improved. The additive is Li2O2And when the concentration is 0.005-0.02M, the first-effect retention rate can be improved simultaneously. The additive is Li2C4O4And when the concentration is 0.02-0.2M, the first-effect retention rate can be improved simultaneously. The additive is Li2C3O5And when the concentration is 0.01-0.1M, the first-effect retention rate can be improved. The additive is Li2C4O6When the concentration is 0.005-0.2M, the first-effect retention rate can be improved.
Claims (9)
1. A lithium-supplement type lithium ion battery electrolyte is characterized by comprising: solvents, electrolytes and additives; the electrolyte may be at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, N-dialkylpyrrolidinium lithium salt, lithium difluorooxalato borate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium N-ethylpyrrolidinium tetrafluoroborate; the additive is selected from LiN3、Li2O2、Li2O、Li2C4O4、Li2C2O4、Li2C3O5、Li2C4O6And LixSyAt leastWherein x is more than or equal to 1 and less than or equal to 10, and y is more than or equal to 1 and less than or equal to 10.
2. The lithium-supplement lithium ion battery electrolyte of claim 1, wherein the molar ratio of the electrolyte to the additive is 1: (0.001-0.2).
3. The lithium-replenishing lithium ion battery electrolyte of claim 2, wherein the molar ratio of the electrolyte to the additive is 1: (0.005-0.2), preferably 1: (0.05-0.08).
4. The lithium ion battery electrolyte according to any one of claims 1 to 3, wherein the solvent is an organic solvent, preferably at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl acetate, methyl acetate, methylethyl carbonate, glutaronitrile, and tetrahydrofuran.
5. The lithium-supplement type lithium ion battery electrolyte according to any one of claims 1 to 4, wherein the concentration of the electrolyte is 0.0001 to 5M, preferably 0.5 to 5M.
6. The lithium-supplement type lithium ion battery electrolyte according to any one of claims 1 to 5, wherein the concentration of the additive is 0.005 to 0.2M, preferably 0.05 to 0.08M.
7. The lithium ion battery electrolyte according to any one of claims 1 to 6, wherein the concentration of the additive is 0.005 to 0.2M, preferably 0.05 to 0.08M, when the electrolyte concentration is 1M.
8. The lithium ion battery electrolyte according to any one of claims 1 to 7, further comprising at least one of vinylene carbonate and fluorinated vinylene carbonate; the total volume of the vinylene carbonate and the fluorinated vinylene carbonate is 0.005-2% of the volume of the solvent.
9. A lithium ion battery, comprising: a positive electrode, a negative electrode, and the lithium-replenishing lithium ion battery electrolyte of any one of claims 1-8.
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