CN114899478A - Carbazole nonaqueous electrolyte, preparation method thereof and lithium ion battery - Google Patents
Carbazole nonaqueous electrolyte, preparation method thereof and lithium ion battery Download PDFInfo
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- CN114899478A CN114899478A CN202210543576.7A CN202210543576A CN114899478A CN 114899478 A CN114899478 A CN 114899478A CN 202210543576 A CN202210543576 A CN 202210543576A CN 114899478 A CN114899478 A CN 114899478A
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 116
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 21
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 21
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims abstract description 20
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 52
- 239000008151 electrolyte solution Substances 0.000 claims description 23
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 150000005678 chain carbonates Chemical class 0.000 claims description 10
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000007784 solid electrolyte Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- 229910013733 LiCo Inorganic materials 0.000 claims description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 3
- 229910011570 LiFe 1-x Inorganic materials 0.000 claims description 3
- 229910015645 LiMn Inorganic materials 0.000 claims description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 3
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 3
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 3
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 238000005524 ceramic coating Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 0.000 claims 2
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 7
- 210000001787 dendrite Anatomy 0.000 description 7
- 230000010287 polarization Effects 0.000 description 5
- 239000002120 nanofilm Substances 0.000 description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002904 solvent Substances 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
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a carbazole nonaqueous electrolyte, which comprises lithium salt, a nonaqueous organic solvent and an additive, wherein the additive is one or a mixture of more of carbazole, N-ethyl carbazole and vinyl carbazole, and the weight percentage content of the additive is 0.25-1.0 wt%. The concentration of lithium salt was 1M. The invention also discloses a preparation method of the carbazole nonaqueous electrolyte, and a lithium ion battery containing the carbazole nonaqueous electrolyte. By adopting the carbazole non-aqueous electrolyte, the preparation method thereof and the lithium ion battery, the invention can solve the problems of low charging and discharging times, low coulombic efficiency and potential safety hazard of the existing electrolyte.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a carbazole nonaqueous electrolyte, a preparation method thereof and a lithium ion battery.
Background
With the development of high-power electronic devices such as electric vehicles, it has been difficult for conventional batteries to meet the requirements for energy density thereof. Lithium metal anode batteries (LMBs) are considered to be the most potential next generation batteries for applications due to their ultra-high theoretical specific capacity (3860mAh/g) and lowest electrochemical potential (-3.04V vs. rhe). However, metallic lithium is likely to form dendrites during repeated deposition and exfoliation, and to react with an electrolyte to form inactive lithium, thereby reducing the number of charge and discharge, coulombic efficiency, and safety. These problems severely limit the application of lithium metal batteries.
Disclosure of Invention
The invention aims to provide a carbazole non-aqueous electrolyte, which solves the problems of low charging and discharging times, low coulombic efficiency and potential safety hazard of the existing electrolyte. The invention also aims to provide a preparation method of the carbazole nonaqueous electrolyte and a lithium ion battery containing the carbazole nonaqueous electrolyte.
In order to achieve the purpose, the invention provides a carbazole nonaqueous electrolytic solution, which comprises lithium salt, a nonaqueous organic solvent and an additive, wherein the additive is one or a mixture of more of carbazole, N-ethyl carbazole and vinyl carbazole, and the weight percentage content of the additive is 0.25-1.0 wt%;
the structural formula of carbazole is
The structure of the N-ethyl carbazole is
The structural formula of the vinyl carbazole is
Preferably, the concentration of the lithium salt is 1M; the lithium salt being LiPF 6 、LiBF 4 、LiBOB、LiDFOB、LiSbF 6 、LiAsF 6 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 C 2 F 5 ) 2 、LiC(SO 2 CF 3 ) 3 Or LiN (SO) 2 F) 2 One or a mixture of several of them.
Preferably, the non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, and the volume ratio of the cyclic carbonate to the chain carbonate is 1:2-2: 1; the cyclic carbonate is one or a mixture of more of ethylene carbonate, propylene carbonate or butylene carbonate, and the chain carbonate is one or a mixture of more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate.
The preparation method of the carbazole nonaqueous electrolyte comprises the following steps:
s1, in a glove box, H 2 O<0.1ppm，O 2 <0.1ppm, weighing a proper amount of lithium salt, and dissolving the lithium salt in a nonaqueous organic solution, wherein the concentration of the lithium salt is 1M, so as to obtain a substrate electrolyte;
and S2, adding an additive with the mass percentage of 0.25-1.0 wt% into the base electrolyte, and uniformly stirring to obtain the carbazole nonaqueous electrolyte.
A lithium ion battery containing the carbazole nonaqueous electrolyte prepared by the preparation method comprises a battery shell, and a positive electrode, a negative electrode, a diaphragm and the electrolyte which are positioned in the battery shell.
Preferably, the positive electrode includes a positive electrode current collector and a positive electrode material on the positive electrode current collector, and the positive electrode material includes a positive electrode active material.
Preferably, the positive active material is LiCoO 2 、LiNiO 2 、LiMn 2 O 4 、LiCo 1-y M y O 2 、LiNi 1-y M y O 2 、LiMn 2-y M y O 4 And LiNi x Co y Mn z M 1-x-y-z O 2 One or a mixture of several of them; wherein M is one or a mixture of more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti, y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is less than or equal to 1.
Preferably, the positive active material is LiFe 1-x M x PO 4 Wherein M is one or a mixture of more of Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti, and x is more than or equal to 0 and less than 1.
Preferably, the negative electrode comprises a negative electrode current collector and a negative electrode material positioned on the negative electrode current collector, and the negative electrode material is one or a mixture of more of graphite, hard carbon, soft carbon, a silicon-carbon composite material, a silicon-oxygen-carbon composite material, metal lithium and an alloy of the metal lithium.
Preferably, the separator is one or more of a polyolefin porous membrane, a nonwoven fabric, a fiber coating, a ceramic coating, and an inorganic solid electrolyte coating.
According to the carbazole non-aqueous electrolyte, the preparation method thereof and the lithium ion battery, the vinylcarbazole additive can be self-polymerized into a Polyvinylcarbazole (PVK) high-molecular film in the electrolyte, and the high-molecular film further decomposes LiN with high lithium conductivity, so that the migration of lithium ions is promoted, and the growth of lithium dendrites is inhibited; because lithium dendrite is inhibited, the performances of the full battery such as stability, rate and the like are also improved. The vinylcarbazole additive generates a solid electrolyte interface (solid electrolyte interface) with high lithium conductivity on the surface of the metal anode, and the SEI inhibits the growth of lithium dendrites and improves the cycle efficiency of the battery. The vinyl carbazole additive has the improvement effect on the anode and the cathode, and the overall performance of the lithium ion battery is improved.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a cycle life diagram of a symmetric lithium battery prepared from a carbazole nonaqueous electrolyte and a preparation method thereof and a lithium ion battery implementing the electrolyte 1 according to the present invention;
FIG. 2 is a cycle life diagram of a lithium symmetric battery prepared by using a carbazole nonaqueous electrolyte and a preparation method thereof and a lithium ion battery implementing the electrolyte 2 according to the present invention;
FIG. 3 is a cycle life diagram of a lithium symmetric battery prepared by using a carbazole nonaqueous electrolyte and a preparation method thereof and a lithium ion battery implementing the electrolyte 3 according to the present invention;
FIG. 4 is a cycle life diagram of a lithium symmetric battery prepared by using a carbazole nonaqueous electrolyte and a preparation method thereof and a lithium ion battery implementing the electrolyte 4 according to the present invention;
FIG. 5 is a cycle life diagram of a symmetric lithium battery prepared using a carbazole nonaqueous electrolyte and a preparation method thereof, and a lithium ion battery implementing electrolyte 5 according to the present invention;
FIG. 6 is a cycle life diagram of a lithium symmetric battery prepared by using a carbazole nonaqueous electrolyte and a preparation method thereof and a lithium ion battery implementing the electrolyte 6 according to the present invention;
FIG. 7 is a cycle life diagram of a symmetric lithium battery prepared using a carbazole nonaqueous electrolyte and a preparation method thereof, and a lithium ion battery implementing the electrolyte 7 of the present invention;
FIG. 8 is a cycle life diagram of a symmetric lithium battery prepared using a carbazole nonaqueous electrolyte and a preparation method thereof according to the present invention, and a lithium ion battery comparative electrolyte 1;
fig. 9 is a cycle performance diagram of a full cell prepared by using the carbazole nonaqueous electrolytic solution and the preparation method thereof, and the electrolyte 1 implemented by the lithium ion battery and the comparative electrolyte 1.
Detailed Description
A carbazole nonaqueous electrolytic solution comprises a lithium salt, a nonaqueous organic solvent and an additive. The additive is one of carbazole, N-ethyl carbazole or vinyl carbazole, and the weight percentage content of the additive is 0.25-1.0 wt%.
The structural formula of carbazole is
The structure of the N-ethyl carbazole is
The structural formula of the vinyl carbazole is
The vinyl carbazole additive can self-polymerize into a polyvinyl carbazole (PVK) high-molecular film in the electrolyte, and the high-molecular film further decomposes LiN with high lithium conductivity, so that the migration of lithium ions is promoted, and the growth of lithium dendrites is inhibited; because lithium dendrite is inhibited, the performances of the full battery such as stability, rate and the like are also improved. The vinylcarbazole additive generates a solid electrolyte interface (solid electrolyte interface) with high lithium conductivity on the surface of the metal anode, and the SEI inhibits the growth of lithium dendrites and improves the cycle efficiency of the battery. The vinyl carbazole additive has the improvement effect on the anode and the cathode, and the overall performance of the lithium ion battery is improved.
The concentration of lithium salt was 1M. The lithium salt being LiPF 6 、LiBF 4 、LiBOB、LiDFOB、LiSbF 6 、LiAsF 6 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 C 2 F 5 ) 2 、LiC(SO 2 CF 3 ) 3 Or LiN (SO) 2 F) 2 One or a mixture of several of them.
The non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, and the volume ratio of the cyclic carbonate to the chain carbonate is 1:2-2: 1; the cyclic carbonate is one or a mixture of more of ethylene carbonate, propylene carbonate or butylene carbonate, and the chain carbonate is one or a mixture of more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate. The mixed solution of the cyclic carbonate organic solvent with high dielectric constant and the chain carbonate organic solvent with low viscosity is used as the solvent of the lithium ion battery electrolyte, so that the mixed solution of the organic solvents simultaneously has high ionic conductivity, high dielectric constant and low viscosity.
The preparation method of the carbazole nonaqueous electrolyte comprises the following steps:
s1, in a glove box, H 2 O<0.1ppm，O 2 <0.1ppm, weighing a proper amount of lithium salt, and dissolving the lithium salt in a nonaqueous organic solution, wherein the concentration of the lithium salt is 1M, so as to obtain a substrate electrolyte;
and S2, adding an additive with the mass percentage of 0.25-1.0 wt% into the base electrolyte, and uniformly stirring to obtain the carbazole nonaqueous electrolyte.
A lithium ion battery containing the carbazole nonaqueous electrolyte comprises a battery shell, and a positive electrode, a negative electrode, a diaphragm and the electrolyte which are positioned in the battery shell.
The positive electrode includes a positive current collector and a positive electrode material on the positive current collector, the positive electrode material including a positive active material.
The positive active material is LiCoO 2 、LiNiO 2 、LiMn 2 O 4 、LiCo 1-y M y O 2 、LiNi 1-y M y O 2 、LiMn 2-y M y O 4 And LiNi x Co y Mn z M 1-x-y-z O 2 One or a mixture of several of them; wherein M is one or a mixture of more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti, y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is less than or equal to 1.
Alternatively, the positive electrode active material is LiFe 1-x M x PO 4 Wherein M is one or a mixture of more of Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti, and x is more than or equal to 0 and less than 1.
The negative electrode comprises a negative electrode current collector and a negative electrode material positioned on the negative electrode current collector, wherein the negative electrode material is one or a mixture of more of graphite, hard carbon, soft carbon, a silicon-carbon composite material, a silicon-oxygen-carbon composite material, metal lithium and an alloy of the metal lithium.
The separator is one or more of polyolefin porous membrane, non-woven fabric, fiber coating, ceramic coating and inorganic solid electrolyte coating.
The technical solution of the present invention is further illustrated by the accompanying drawings and examples.
Example 1
In a glove box (H) 2 O<0.1ppm，O 2 <0.1ppm), an appropriate amount of lithium hexafluorophosphate (LiPF) was weighed 6 ) And dissolving the electrolyte in a non-aqueous organic solution to obtain a base electrolyte.
Lithium salt concentration: 1M lithium hexafluorophosphate (LiPF) 6 )；
Non-aqueous organic solvent: ethylene Carbonate (EC), a mixed solvent of dimethyl carbonate (DMC) 1:1(v: v);
0.25 wt% of vinylcarbazole R is added into the base electrolyte 3 The compound shown was uniformly stirred to obtain an electrolyte solution 1.
Example 2
An electrolyte was prepared as described in example 1, except that the electrolyte was present in the baseAdding 0.25 wt% of carbazole R 1 Thus, working electrolyte 2 was obtained.
Example 3
An electrolyte was prepared as described in example 1, except that 0.25 wt% N-ethylcarbazole R was added to the base electrolyte 2 Thus, working electrolyte 3 was obtained.
Example 4
An electrolyte was prepared as described in example 1, except that 0.5 wt% vinylcarbazole R was added to the base electrolyte 3 Thus, working electrolyte 4 was obtained.
Example 5
An electrolyte was prepared as described in example 1, except that 1.0 wt% vinylcarbazole R was added to the base electrolyte 3 Thus, working electrolyte 5 was obtained.
Example 6
An electrolyte was prepared by the method described in example 1 except that the mixed solvent ratio of vinyl carbonate (EC) to dimethyl carbonate (DMC) in the base electrolyte was 2:1(v: v), to give an example electrolyte 6.
Example 7
An electrolyte was prepared by the method described in example 1 except that the mixed solvent ratio of vinyl carbonate (EC) to dimethyl carbonate (DMC) in the base electrolyte was 1:2(v: v), to give an example electrolyte 7.
Comparative example 1
Comparative example a base electrolyte prepared by the method described in example 1 was used as comparative electrolyte 1.
Lithium batteries were prepared using the above-described example electrolytes 1 to 7 and the comparative electrolyte 1.
The preparation method of the lithium battery comprises the following steps:
lithium symmetrical cell: in a glove box (H) 2 O<0.1ppm，O 2 <0.1ppm), sequentially assembling the positive electrode shell → the lithium sheet → the electrolyte → the diaphragm → the electrolyte → the lithium sheet → the stainless steel gasket → the negative electrode shell from bottom to top, and then transferring to a tablet press for punching and packaging to obtain the finished lithium symmetric battery.
All-battery: in a glove box (H) 2 O<0.1ppm，O 2 <0.1ppm), sequentially assembling the positive electrode shell → NCM622 pole piece → electrolyte → diaphragm → lithium piece → stainless steel gasket → spring piece → negative electrode shell from bottom to top, and then transferring to a tablet press for punching and packaging to obtain the finished full cell.
Electrochemical performance tests were performed on the assembled cells using novalr test equipment. The specific experimental process is as follows: assembling a lithium symmetric battery by taking the lithium sheets as positive and negative electrodes to perform constant current charge and discharge test; lithium sheet as negative electrode, NCM811 (LiNi) 0.8 Co 0.1 Mn 0.1 O 2 ) Is a positive active material, and is matched and assembled into a full cell for constant current charge and discharge test.
Fig. 1 is a cycle life diagram of a lithium symmetric battery prepared from a carbazole nonaqueous electrolytic solution and a preparation method thereof and a lithium ion battery implementation electrolyte 1 of the invention, fig. 2 is a cycle life diagram of a lithium symmetric battery prepared from a carbazole nonaqueous electrolytic solution and a preparation method thereof and a lithium ion battery implementation electrolyte 2 of the invention, fig. 3 is a cycle life diagram of a lithium symmetric battery prepared from a carbazole nonaqueous electrolytic solution and a preparation method thereof and a lithium ion battery implementation electrolyte 3 of the invention, and fig. 8 is a cycle life diagram of a lithium symmetric battery prepared from a carbazole nonaqueous electrolytic solution and a preparation method thereof and a lithium ion battery comparison electrolyte 1 of the invention. As shown in the figure, the polarization degree of the lithium symmetric battery prepared by using the electrolyte 1 is still small after the battery is cycled for more than 350 hours, the polarization of the lithium symmetric battery prepared by using the electrolyte 2 is large after the battery is cycled for 230 hours, and the polarization of the lithium symmetric battery prepared by using the electrolyte 3 is large after the battery is cycled for 240 hours. The lithium symmetrical cell prepared with comparative electrolyte 1 shows severe polarization after 120 hours of cycling. Thus, carbazole R is added to the electrolyte 1 N-ethylcarbazole R 2 Or vinylcarbazole R 3 The cycle life of the battery can be effectively prolonged.
FIG. 4 shows a carbazole nonaqueous electrolyte and a preparation method thereofThe method and the lithium ion battery implement electrolyte 4, and fig. 5 is a cycle life diagram of the lithium symmetric battery prepared by the carbazole non-aqueous electrolyte and the preparation method thereof, and the lithium ion battery implement electrolyte 5. As shown, the symmetric lithium batteries prepared using the example electrolyte 4 and the example electrolyte 5 enable the degree of polarization to remain small after cycling of the batteries for more than 350 hours. Thus, modification of vinylcarbazole R in electrolyte 3 The concentration of the additive and the cycle life of the obtained lithium symmetrical battery are effectively prolonged. It can be seen that the vinylcarbazole R is present in different concentrations 3 The additive has good effect on prolonging the cycle performance of the lithium symmetrical battery.
Fig. 6 is a cycle life diagram of a lithium symmetric battery prepared by using a carbazole nonaqueous electrolytic solution and a preparation method thereof and a lithium ion battery implementation electrolyte solution 6 of the present invention, and fig. 7 is a cycle life diagram of a lithium symmetric battery prepared by using a carbazole nonaqueous electrolytic solution and a preparation method thereof and a lithium ion battery implementation electrolyte solution 7 of the present invention. As shown, the cycle life of the lithium symmetrical battery prepared by implementing the electrolyte 6 and the electrolyte 7 can reach 270 hours, which is obviously improved compared with the comparative electrolyte 1. Thus, the vinylcarbazole R is obtained under the condition of different proportions of the nonaqueous organic solvent 3 The additive can still obviously prolong the cycle life of the lithium symmetrical battery.
Fig. 9 is a cycle performance diagram of a full cell prepared by using the carbazole nonaqueous electrolytic solution and the preparation method thereof, and the electrolyte 1 implemented by the lithium ion battery and the comparative electrolyte 1. As shown in the figure, the cycle stability of the full battery assembled by using the electrolyte 1 is greatly improved, the capacity retention rate of 90.2% is still maintained after 150 cycles of cycle, and the specific capacity attenuation is slow.
Therefore, the carbazole non-aqueous electrolyte, the preparation method thereof and the lithium ion battery can solve the problems of low charging and discharging times, low coulombic efficiency and potential safety hazard of the conventional electrolyte.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (10)
1. A carbazole nonaqueous electrolytic solution is characterized in that: the lithium salt, the non-aqueous organic solvent and the additive are included, the additive is one or a mixture of more of carbazole, N-ethyl carbazole and vinyl carbazole, and the weight percentage content of the additive is 0.25-1.0 wt%;
the structural formula of carbazole is
The structure of the N-ethyl carbazole is
The structural formula of the vinyl carbazole is
2. The carbazole nonaqueous electrolytic solution of claim 1, wherein: the concentration of the lithium salt is 1M; the lithium salt being LiPF 6 、LiBF 4 、LiBOB、LiDFOB、LiSbF 6 、LiAsF 6 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 C 2 F 5 ) 2 、LiC(SO 2 CF 3 ) 3 Or LiN (SO) 2 F) 2 One or a mixture of several of them.
3. The carbazole nonaqueous electrolytic solution of claim 1, wherein: the non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, and the volume ratio of the cyclic carbonate to the chain carbonate is 1:2-2: 1; the cyclic carbonate is one or a mixture of more of ethylene carbonate, propylene carbonate or butylene carbonate, and the chain carbonate is one or a mixture of more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate.
4. The method for preparing a carbazole nonaqueous electrolytic solution according to any one of claims 1 to 3, characterized by comprising the steps of:
s1, in a glove box, H 2 O<0.1ppm，O 2 <0.1ppm, weighing a proper amount of lithium salt, and dissolving the lithium salt in a nonaqueous organic solution, wherein the concentration of the lithium salt is 1M, so as to obtain a substrate electrolyte;
and S2, adding an additive with the mass percentage of 0.25-1.0 wt% into the base electrolyte, and uniformly stirring to obtain the carbazole nonaqueous electrolyte.
5. A lithium ion battery comprising the carbazole nonaqueous electrolytic solution prepared in claim 4, characterized in that: comprises a battery shell, a positive electrode, a negative electrode, a diaphragm and electrolyte which are positioned in the battery shell.
6. The carbazole nonaqueous electrolytic solution of claim 5, wherein: the positive electrode comprises a positive electrode current collector and a positive electrode material positioned on the positive electrode current collector, wherein the positive electrode material comprises a positive electrode active material.
7. The carbazole nonaqueous electrolytic solution of claim 6, wherein: the positive active material is LiCoO 2 、LiNiO 2 、LiMn 2 O 4 、LiCo 1-y M y O 2 、LiNi 1-y M y O 2 、LiMn 2-y M y O 4 And LiNi x Co y Mn z M 1-x-y-z O 2 One or a mixture of several of them; wherein M is one or a mixture of more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti, y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is less than or equal to 1.
8. The carbazole nonaqueous electrolytic solution of claim 6, wherein: the positive active material is LiFe 1-x M x PO 4 Wherein M is one or a mixture of more of Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti, and x is more than or equal to 0 and less than 1.
9. The carbazole nonaqueous electrolytic solution of claim 5, wherein: the negative electrode comprises a negative electrode current collector and a negative electrode material positioned on the negative electrode current collector, wherein the negative electrode material is one or a mixture of more of graphite, hard carbon, soft carbon, a silicon-carbon composite material, a silicon-oxygen-carbon composite material, metal lithium and an alloy of the metal lithium.
10. The carbazole nonaqueous electrolytic solution of claim 5, wherein: the diaphragm is one or more of polyolefin porous membrane, non-woven fabric, fiber coating, ceramic coating and inorganic solid electrolyte coating.
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