CN117525544A - Lithium-sodium co-intercalation double-ion battery based on hard carbon material - Google Patents
Lithium-sodium co-intercalation double-ion battery based on hard carbon material Download PDFInfo
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- CN117525544A CN117525544A CN202311662488.XA CN202311662488A CN117525544A CN 117525544 A CN117525544 A CN 117525544A CN 202311662488 A CN202311662488 A CN 202311662488A CN 117525544 A CN117525544 A CN 117525544A
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- lithium
- sodium
- positive electrode
- negative electrode
- hard carbon
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 47
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 35
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000009830 intercalation Methods 0.000 title claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 47
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 20
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 20
- 239000013543 active substance Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 12
- 239000001989 lithium alloy Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 18
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 12
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- SCMJJGWRVSLYLK-UHFFFAOYSA-N 4-phenoxycarbonylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)OC1=CC=CC=C1 SCMJJGWRVSLYLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 3
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 claims description 3
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 claims description 3
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 claims description 3
- ZQDZSGHAIZKNHJ-UHFFFAOYSA-N trisodium difluoro oxalate borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-].FOC(=O)C(=O)OF ZQDZSGHAIZKNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 9
- 230000009977 dual effect Effects 0.000 claims 8
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000011229 interlayer Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000006183 anode active material Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920006215 polyvinyl ketone Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium-sodium co-intercalation double-ion battery based on a hard carbon material, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode comprises a metal lithium sheet, a lithium alloy sheet or a positive electrode sheet, the positive electrode sheet comprises a positive electrode current collector and a positive electrode active substance coated on the positive electrode current collector, and the positive electrode active substance is a lithium-containing material; the negative electrode comprises a negative electrode plate, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode active substance coated on the negative electrode current collector, and the negative electrode active substance is hard carbon; the electrolyte comprises a solvent, a metal salt and an additive, wherein the metal salt comprises sodium salt or a mixture of lithium salt and sodium salt. The invention can maximally utilize the active sites of the hard carbon material, sodium ions are mainly adsorbed on the mesopores, micropores and end surfaces of the hard carbon material in the battery charging process, and small micropores and interlayer sites are filled with lithium ions with smaller volume, so that the storage capacity of the material is greatly increased, and the capacity of the battery is remarkably improved. Meanwhile, the method is simple to operate and is beneficial to realizing industrial production.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a lithium-sodium co-intercalation double-ion battery based on a hard carbon material.
Background
Lithium ion batteries are the main stream of modern energy storage and power batteries, and the negative electrode material is mainly graphite material. Lithium ions are stored between graphite layers in an intercalation mode, the theoretical capacity of the lithium ion battery is 372mAh/g, but the capacity of the lithium ion battery is limited in the current lifting space, and the further lifting of the energy density of the lithium ion battery is severely restricted. On the other hand, sodium ion batteries have been receiving extensive attention and research as a novel battery with low cost, good quick charge performance, and good high and low temperature performance. The negative electrode material of the sodium ion battery generally uses hard carbon, and the maximum gram capacity of the current commercial hard carbon material reaches 340mAh/g, but still has larger lifting space. Because of the larger atomic radius of sodium ions, most of storage sites are end faces, micropores, gaps and the like of hard carbon materials. Therefore, how to develop a battery that can fully utilize various storage sites of carbon materials, such as layers, pores, end faces, etc., has great significance in improving the gram capacity and energy density of the battery.
However, there is no battery product on the market that can fully utilize these storage sites, which is certainly a great challenge. Therefore, developing a new battery structure to fully utilize various storage sites of carbon materials and to improve the gram capacity and energy density of the battery has become a current urgent problem to be solved.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a lithium-sodium co-intercalation dual-ion battery based on a hard carbon material, which can significantly improve the capacity of the battery.
In order to achieve the above object, the invention provides a lithium-sodium co-intercalation dual-ion battery based on hard carbon material, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode comprises a metal lithium sheet, a lithium alloy sheet or a positive electrode sheet, the positive electrode sheet comprises a positive electrode current collector and a positive electrode active substance coated on the positive electrode current collector, and the positive electrode active substance is a lithium-containing material;
the negative electrode comprises a negative electrode plate, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode active substance coated on the negative electrode current collector, and the negative electrode active substance is hard carbon;
the electrolyte includes a solvent, a metal salt including a sodium salt or a mixture of a lithium salt and a sodium salt, and an additive.
Compared with the prior art, the lithium-sodium co-intercalation double-ion battery based on the hard carbon material adopts the anode active material as hard carbon, the anode comprises a metal lithium sheet, a lithium alloy sheet or an anode sheet, the anode active material is a lithium-containing material, the sodium salt or the mixture of the lithium salt and the sodium salt is used as electrolyte of electrolyte, active sites of the hard carbon material are utilized to the greatest extent, sodium ions are mainly adsorbed on mesopores, micropores and end surfaces of the hard carbon material in the charging process of the battery, small micropores and interlayer sites are filled by lithium ions with smaller volume, the storable capacity of the material is greatly increased, and the capacity of the battery is remarkably improved. Meanwhile, the method is simple to operate and is beneficial to realizing industrial production.
In some embodiments, the lithium-containing material is selected from at least one of lithium oxide, lithium salt.
In some embodiments, the lithium salt comprises at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganate.
In some embodiments, the lithium alloy sheet is selected from one of a lithium aluminum alloy, a lithium magnesium alloy, a lithium titanium alloy, a lithium copper alloy, and a lithium zinc alloy.
In some embodiments, the positive electrode sheet includes the positive electrode current collector and a positive electrode material coated on the positive electrode current collector, the positive electrode material including the positive electrode active material, a conductive agent, and a binder, the mass ratio of the positive electrode active material, the conductive agent, and the binder being 70 to 96:2-15:2-15.
In some embodiments, the negative electrode sheet includes the negative electrode current collector and a negative electrode material coated on the negative electrode current collector, the negative electrode material including the negative electrode active material, a conductive agent, and a binder, the mass ratio of the negative electrode active material, the conductive agent, and the binder being 80-98:1-10:1-10.
In some embodiments, the separator is selected from at least one of a polyolefin separator or a glass fiber separator.
In some embodiments, the solvent is selected from one or more of PC (propylene carbonate), EC (ethylene carbonate), DEC (diethyl carbonate), DME (ethylene glycol dimethyl ether) and DOL (dioxolane);
the additive is at least one selected from fluoroethylene carbonate (FEC), vinylene Carbonate (VC), 1, 3-Propane Sultone (PS), poly (phenyl terephthalate) (PST), ethylene sulfate (DTD) and sodium difluoro oxalate borate (NaDFOB).
In some embodiments, the sodium salt is selected from at least one of sodium hexafluorophosphate, sodium perchlorate, sodium difluorophosphate, sodium bisoxalato borate, sodium difluorooxalato borate, sodium bistrifluoromethylsulfonylimide, and sodium bisfluoro-sulfonylimide.
In some embodiments, the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato phosphate, lithium tetrafluoroborate, lithium tetrafluorooxalato phosphate, lithium bistrifluoromethylsulfonimide, lithium bisfluorosulfonyl imide, or lithium difluorobismalonate.
Drawings
Fig. 1 is a charge-discharge curve of the battery test procedure prepared in example 1 and comparative examples 1-2.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
The invention provides a lithium-sodium co-intercalation double-ion battery based on a hard carbon material, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode comprises a metal lithium sheet, a lithium alloy sheet or a positive electrode sheet, the positive electrode sheet comprises a positive electrode current collector and a positive electrode active substance coated on the positive electrode current collector, and the positive electrode active substance is a lithium-containing material; the negative electrode comprises a negative electrode plate, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode active substance coated on the negative electrode current collector, and the negative electrode active substance is hard carbon; the electrolyte comprises a solvent, a metal salt and an additive, wherein the metal salt comprises sodium salt or a mixture of lithium salt and sodium salt.
The lithium-sodium co-intercalation double-ion battery based on the hard carbon material adopts the anode active material as hard carbon, the anode comprises a metal lithium sheet, a lithium alloy sheet or an anode sheet, the anode active material is a lithium-containing material, the sodium salt or a mixture of the lithium salt and the sodium salt is used as electrolyte of electrolyte, active sites of the hard carbon material are utilized to the greatest extent, sodium ions are mainly adsorbed on mesopores, micropores and end surfaces of the hard carbon material in the charging process of the battery, small micropores and interlayer sites are filled by lithium ions with smaller volume, and the storable capacity of the material is greatly increased, so that the capacity of the battery is remarkably improved. Meanwhile, the method is simple to operate and is beneficial to realizing industrial production.
The positive electrode includes a metal lithium sheet, a lithium alloy sheet or a positive electrode sheet, that is, a metal lithium sheet or a lithium alloy sheet may be used as the positive electrode, or a positive electrode sheet may be prepared by coating a positive electrode material containing a lithium material on the surface of a positive electrode current collector, and in one embodiment, a metal lithium sheet is used as the positive electrode, but is not limited thereto.
In a preferred embodiment, the lithium alloy sheet is selected from the group consisting of lithium aluminum alloys, lithium magnesium alloys, lithium titanium alloys, lithium copper alloys, lithium zinc alloys, and the like.
In a preferred embodiment, the positive electrode sheet includes a positive electrode current collector and a positive electrode material coated on the positive electrode current collector, and the present invention does not limit the positive electrode current collector, but preferably includes a copper sheet, but may also include an aluminum sheet, a zinc sheet, a separator, and the like.
In a preferred embodiment, the positive electrode material includes a positive electrode active material, a conductive agent, and a binder. Further, the mass ratio of the positive electrode active material, the conductive agent and the binder is 70-96:2-15:2-15. As an example, the mass ratio of the positive electrode active material, the conductive agent, and the binder is 96:2:2, but not limited thereto.
In a preferred embodiment, the conductive agent is selected from at least one of conductive carbon black, natural graphite, artificial graphite, carbon nanotubes, graphene.
In a preferred embodiment, the binder is selected from at least one of SBR rubber, acrylic acid esters, polyolefin, polyvinyl alcohol, polyvinyl ketone, polyvinylidene fluoride, carboxymethyl cellulose, polytetrafluoroethylene.
In a preferred embodiment, the positive electrode active material is a lithium-containing material selected from at least one of lithium oxide and lithium salt. It can be understood that the radius of lithium is small, sodium ions are mainly adsorbed and desorbed in the micropores of the hard carbon in the charge and discharge process, lithium ions are mainly intercalated and deintercalated between the layers of the hard carbon, and the storable capacity of the material is greatly increased.
In a preferred embodiment, the lithium oxide is selected from Li 2 O、Li 2 O 2 Etc.
In a preferred embodiment, the lithium salt comprises at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganate. As an example, the lithium salt is lithium cobaltate, or a mixture of lithium manganate and lithium iron phosphate, or a mixture of lithium cobaltate, lithium manganate, lithium iron phosphate and lithium nickel cobalt manganate, or the like.
In a preferred embodiment, the invention also provides a preparation method of the positive plate, which comprises the following steps: the positive electrode active material, the conductive agent and the binder are mixed according to the mass ratio of 70-96:2-15:2-15, and then coating the mixture on a positive electrode current collector, and drying to obtain a positive electrode plate, wherein the drying temperature is 80-150 ℃ and the drying time is 2-24h.
For the negative electrode, the negative electrode comprises a negative electrode sheet, the negative electrode sheet comprises a negative electrode current collector and a negative electrode material coated on the negative electrode current collector, the negative electrode current collector is not limited by the invention, and the negative electrode current collector is preferably an aluminum sheet, but can also be a copper sheet, a zinc sheet, a separator and the like.
In a preferred embodiment, the anode material includes an anode active material, a conductive agent, and a binder. Further, the mass ratio of the anode active material, the conductive agent and the binder is 80-98:1-10:1-10. As an example, the mass ratio of the anode active material, the conductive agent, and the binder is 94:3:3, but not limited thereto.
In a preferred embodiment, the conductive agent is selected from at least one of conductive carbon black, natural graphite, artificial graphite, carbon nanotubes, graphene.
In a preferred embodiment, the binder is selected from at least one of SBR rubber, acrylic acid esters, polyolefin, polyvinyl alcohol, polyvinyl ketone, polyvinylidene fluoride, carboxymethyl cellulose, polytetrafluoroethylene.
In a preferred embodiment, the invention also provides a preparation method of the negative plate, which comprises the following steps: the negative electrode active material, the conductive agent and the binder are mixed according to the mass ratio of 80-98:1-10:1-10, then coating the mixture on a negative electrode current collector, and drying to obtain the negative electrode, wherein the drying temperature is 80-120 ℃ and the drying time is 2-24h.
The separator is not particularly limited in the present invention, and a separator conventional in the art may be used. In a preferred embodiment, the separator is selected from at least one of a polyolefin separator or a glass fiber separator, preferably a polyolefin separator or a glass fiber separator with good affinity.
For the electrolyte, the electrolyte includes a solvent, a metal salt, and an additive.
In a preferred embodiment, the solvent is selected from one or more of PC (propylene carbonate), EC (ethylene carbonate), DEC (diethyl carbonate), DME (ethylene glycol dimethyl ether) and DOL (dioxolane), and as an example, the solvent is selected from a mixture of PC, EC, DEC in a mass ratio of 1:1:1, but not limited thereto.
In a preferred embodiment, the additive is at least one selected from fluoroethylene carbonate (FEC), vinylene Carbonate (VC), 1, 3-Propane Sultone (PS), poly (phenyl terephthalate) (PST), ethylene sulfate (DTD), sodium difluoro oxalato borate (nadob), by way of example, but not limitation, fluoroethylene carbonate (FEC).
In a preferred embodiment, the metal salt comprises a sodium salt or a mixture of a lithium salt and a sodium salt. Illustratively, the metal salt is a sodium salt, and in some embodiments, the metal salt is a mixture of a lithium salt and a sodium salt, illustratively, a mixture of sodium hexafluorophosphate and lithium hexafluorophosphate, by adding a lithium salt to the metal salt to provide more lithium ions that intercalate and deintercalate between hard carbon layers.
In a preferred embodiment, the sodium salt is selected from at least one of sodium hexafluorophosphate, sodium perchlorate, sodium difluorophosphate, sodium bisoxalato borate, sodium difluorooxalato borate, sodium bistrifluoromethylsulfonylamino and sodium bisfluorosulfonyl imide.
In a preferred embodiment, the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato phosphate, lithium tetrafluoroborate, lithium tetrafluorooxalato phosphate, lithium bistrifluoromethylsulfonimide, lithium bisfluorosulfonyl imide, or lithium difluorobismalonate.
The invention also provides a preparation method of the battery, which comprises the following steps:
and placing the anode, the diaphragm and the cathode in a shell, adding electrolyte to two sides of the diaphragm, and sealing and fixing the battery.
Example 1
A lithium-sodium co-embedded double-ion battery based on hard carbon material comprises a positive electrode, a negative electrode, a diaphragm and electrolyte,
preparing a positive electrode: adopting a metal lithium sheet as an anode;
preparing a negative electrode: hard carbon, conductive carbon black and SBR rubber are mixed according to the mass ratio of 94:3:3, mixing and pulping, then coating the mixture on the surface of an aluminum sheet of the negative electrode current collector, and drying to obtain the negative electrode, wherein the drying temperature is 100 ℃, and the drying time is 12 hours.
Preparing a diaphragm: cutting Cheng Yuanpian the polyolefin diaphragm for later use;
preparing an electrolyte: in a glove box filled with nitrogen (O2 is less than or equal to 5ppm, H2O is less than or equal to 5 ppm), uniformly mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and Propylene Carbonate (PC) according to a mass ratio of 1:1:1 to obtain 85g of organic solvent, and adding 2g of fluoroethylene carbonate (FEC) as an additive to obtain a mixed solution. Sealing and packaging the mixed solution, placing in a quick freezing room (-4 ℃) for freezing for 2 hours, taking out, slowly adding 13g of sodium hexafluorophosphate into the mixed solution in a glove box (O2 is less than or equal to 5ppm and H2O is less than or equal to 5 ppm) filled with nitrogen, and uniformly mixing to prepare electrolyte;
assembling a battery:
and in a glove box, placing the anode, the diaphragm and the cathode in a shell, adding electrolyte to two sides of the diaphragm, and sealing and fixing to form the battery.
Example 2
A lithium-sodium co-embedded double-ion battery based on hard carbon material comprises a positive electrode, a negative electrode, a diaphragm and electrolyte,
preparing a positive electrode: the positive electrode adopts a positive plate,
mixing a mixture (1:1) of lithium manganate and lithium iron phosphate, carbon nano tubes and polyvinylidene fluoride according to a mass ratio of 95:2.5:2.5, mixing and pulping, then coating the mixture on the surface of a copper sheet of the positive current collector, and drying to obtain a positive plate, wherein the drying temperature is 100 ℃, and drying is carried out for 10 hours;
preparing a negative electrode:
hard carbon, conductive carbon black and SBR rubber are mixed according to the mass ratio of 94:3:3, mixing and pulping, then coating the mixture on the surface of an aluminum sheet of the negative electrode current collector, drying to obtain a negative electrode, and drying at 100 ℃ for 12 hours;
preparing a diaphragm:
cutting Cheng Yuanpian the polyolefin diaphragm for later use;
preparing an electrolyte:
in a glove box filled with nitrogen (O2 is less than or equal to 5ppm, H2O is less than or equal to 5 ppm), uniformly mixing PC (propylene carbonate), diethyl carbonate (DEC) and Propylene Carbonate (PC) according to a mass ratio of 1:2:1 to prepare 85g of organic solvent, and adding 3g of 1, 3-Propane Sultone (PS) as an additive to obtain a mixed solution. Sealing and packaging the mixed solution, placing in a quick freezing room (-4 ℃) for freezing for 2 hours, taking out, slowly adding 10g of sodium hexafluorophosphate and 2g of lithium hexafluorophosphate into the mixed solution in a glove box (O2 is less than or equal to 5ppm and H2O is less than or equal to 5 ppm) filled with nitrogen, and uniformly mixing to prepare an electrolyte;
assembling a battery:
and in a glove box, placing the anode, the diaphragm and the cathode in a shell, adding electrolyte to two sides of the diaphragm, and sealing and fixing to form the battery.
Example 3
A lithium-sodium co-embedded double-ion battery based on hard carbon material comprises a positive electrode, a negative electrode, a diaphragm and electrolyte,
preparing a positive electrode: the positive electrode adopts a positive plate,
li is mixed with 2 O, conductive carbon black and polytetrafluoroethylene according to the mass ratio of 94:3:3, mixing and pulping, then coating the mixture on the surface of a copper sheet of the positive current collector, and drying to obtain a positive plate, wherein the drying temperature is 120 ℃, and drying is carried out for 12 hours;
preparing a negative electrode:
hard carbon, conductive carbon black and polytetrafluoroethylene are mixed according to the mass ratio of 94:3:3, mixing and pulping, then coating the mixture on the surface of an aluminum sheet of the negative electrode current collector, drying to obtain a negative electrode, and drying at 100 ℃ for 12 hours;
preparing a diaphragm:
cutting Cheng Yuanpian the polyolefin diaphragm for later use;
preparing an electrolyte:
in a glove box filled with nitrogen (O2 is less than or equal to 5ppm, H2O is less than or equal to 5 ppm), uniformly mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and Propylene Carbonate (PC) according to a mass ratio of 2:1:1 to prepare 85g of organic solvent, and adding 2g of ethylene sulfate (DTD) as an additive to obtain a mixed solution. Sealing and packaging the mixed solution, placing in a quick freezing room (-4 ℃) for freezing for 2 hours, taking out, slowly adding 13g of sodium difluoro oxalato borate into the mixed solution in a glove box (O2 is less than or equal to 5ppm and H2O is less than or equal to 5 ppm) filled with nitrogen, and uniformly mixing to prepare an electrolyte;
assembling a battery:
and in a glove box, placing the anode, the diaphragm and the cathode in a shell, adding electrolyte to two sides of the diaphragm, and sealing and fixing to form the battery.
Comparative example 1
This comparative example 1 is substantially the same as example 1 except that lithium hexafluorophosphate is used as the electrolyte salt in the electrolyte solution of comparative example 1, while sodium hexafluorophosphate is used as the electrolyte salt in the electrolyte solution of example 1, and the remainder are the same as example 1, and will not be described here.
Comparative example 2
This comparative example 2 is basically the same as example 1 except that a metallic sodium sheet is used as the positive electrode in comparative example 2, a metallic lithium sheet is used as the positive electrode in example 1, and the remainder are the same as example 1, and will not be described here.
The batteries prepared in example 1 and comparative examples 1 to 2 were subjected to a first-turn performance test, and the results are shown in table 1 and fig. 1.
Table 1 first turn performance test results
| Test group | First charge capacity | First discharge capacity | Efficiency of |
| Example 1 | 598.6mAh/g | 440mAh/g | 73.5％ |
| Comparative example 1 | 363mAh/g | 265mAh/g | 73％ |
| Comparative example 2 | 371.3mAh/g | 323mAh/g | 87％ |
As can be seen from the data in table 1 and fig. 1, the first discharge capacity of the lithium-sodium co-intercalation dual-ion battery of the present invention is improved to 440mAh/g, and the efficiency of the present invention is not reduced as compared with the comparative example 1, which indicates that the lithium-sodium co-intercalation dual-ion battery of the present invention can significantly improve the capacity of the battery. The lithium-sodium co-intercalation double-ion battery based on the hard carbon material adopts the anode active material as hard carbon, the anode comprises a metal lithium sheet, a lithium alloy sheet or an anode sheet, the anode active material is a lithium-containing material, the sodium salt or the mixture of the lithium salt and the sodium salt is used as electrolyte of electrolyte, the active site of the hard carbon material is utilized to the greatest extent, sodium ions are mainly adsorbed on mesopores, micropores and end surfaces of the hard carbon material in the charging process of the battery, small micropores and interlayer sites are filled by lithium ions with smaller volume, and the storable capacity of the material is greatly increased, so that the capacity of the battery is remarkably improved. Meanwhile, the method is simple to operate and is beneficial to realizing industrial production.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A lithium-sodium co-embedded double-ion battery based on hard carbon material comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that,
the positive electrode comprises a metal lithium sheet, a lithium alloy sheet or a positive electrode sheet, wherein the positive electrode sheet comprises a positive electrode current collector and a positive electrode active substance coated on the positive electrode current collector, and the positive electrode active substance is a lithium-containing material;
the negative electrode comprises a negative electrode plate, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode active substance coated on the negative electrode current collector, and the negative electrode active substance is hard carbon;
the electrolyte includes a solvent, a metal salt including a sodium salt or a mixture of a lithium salt and a sodium salt, and an additive.
2. The hard carbon material-based lithium sodium co-intercalation dual ion battery of claim 1, wherein the lithium-containing material is selected from at least one of lithium oxide, lithium salt.
3. The hard carbon material-based lithium sodium co-intercalation dual ion battery of claim 2, wherein the lithium salt comprises at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganate.
4. The hard carbon material-based lithium-sodium co-intercalation dual ion battery of claim 1, wherein the lithium alloy sheet is selected from one of lithium aluminum alloy, lithium magnesium alloy, lithium titanium alloy, lithium copper alloy, lithium zinc alloy.
5. The hard carbon material-based lithium-sodium co-intercalation dual ion battery of claim 1, wherein the positive electrode sheet comprises the positive electrode current collector and a positive electrode material coated on the positive electrode current collector, the positive electrode material comprises the positive electrode active material, a conductive agent and a binder, and the mass ratio of the positive electrode active material, the conductive agent and the binder is 70-96:2-15:2-15.
6. The hard carbon material-based lithium-sodium co-intercalation dual ion battery of claim 1, wherein the negative electrode sheet comprises the negative electrode current collector and a negative electrode material coated on the negative electrode current collector, the negative electrode material comprising the negative electrode active material, a conductive agent and a binder, wherein the mass ratio of the negative electrode active material, the conductive agent and the binder is 80-98:1-10:1-10.
7. The hard carbon material based lithium sodium co-intercalation dual ion battery of claim 1, wherein the separator is selected from at least one of a polyolefin separator or a glass fiber separator.
8. The lithium-sodium co-intercalation double ion battery based on hard carbon material according to claim 1, wherein the solvent is selected from one or more of propylene carbonate, ethylene carbonate, diethyl carbonate, ethylene glycol dimethyl ether and dioxolane;
the additive is at least one selected from fluoroethylene carbonate, vinylene carbonate, 1, 3-propane sultone, poly (phenyl terephthalate), vinyl sulfate and sodium difluoro oxalate borate.
9. The hard carbon material-based lithium-sodium co-intercalation dual ion battery of claim 1, wherein the sodium salt is selected from at least one of sodium hexafluorophosphate, sodium perchlorate, sodium difluorophosphate, sodium bisoxalato borate, sodium difluorooxalato borate, sodium bistrifluoromethylsulfonylimide and sodium bisfluoro-sulfonylimide.
10. The hard carbon material-based lithium-sodium co-intercalation dual ion battery of claim 1, wherein the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato phosphate, lithium tetrafluoroborate, lithium tetrafluorooxalato phosphate, lithium bistrifluoromethylsulfonyl imide, lithium bisfluoro-sulfonyl imide, or lithium difluorobismalonate phosphate.
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