CN114792793A - Sodium ion battery additive and high-power sodium ion battery - Google Patents
Sodium ion battery additive and high-power sodium ion battery Download PDFInfo
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- CN114792793A CN114792793A CN202110098328.1A CN202110098328A CN114792793A CN 114792793 A CN114792793 A CN 114792793A CN 202110098328 A CN202110098328 A CN 202110098328A CN 114792793 A CN114792793 A CN 114792793A
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- sodium
- ion battery
- additive
- positive electrode
- cathode
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Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 80
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000000654 additive Substances 0.000 title claims abstract description 55
- 230000000996 additive effect Effects 0.000 title claims abstract description 55
- 239000007774 positive electrode material Substances 0.000 claims abstract description 40
- 239000007773 negative electrode material Substances 0.000 claims abstract description 20
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- -1 polypropylene Polymers 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000006258 conductive agent Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011883 electrode binding agent Substances 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229920000447 polyanionic polymer Polymers 0.000 claims description 6
- 229960003351 prussian blue Drugs 0.000 claims description 6
- 239000013225 prussian blue Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000003013 cathode binding agent Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004026 adhesive bonding Methods 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 239000002194 amorphous carbon material Substances 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 238000005524 ceramic coating Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 150000002895 organic esters Chemical class 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 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
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 150000008053 sultones Chemical class 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 229910014142 Na—O Inorganic materials 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a sodium ion battery additive and a high-power sodium ion battery. The additive is beta-alumina, and the chemical formula of the beta-alumina is M 2 O·xAl 2 O 3 Wherein M is I in the periodic table A Group elements or I B One or more of group elements, wherein x is 5-11; the additive is used as an additive of a positive electrode material and/or a negative electrode material of a sodium-ion battery.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a sodium ion battery additive and a high-power sodium ion battery.
Background
Under the high power application condition (10C, minute-level response time), the cycle service life of a single lithium ion battery system under the actual condition can be greatly reduced, the power type and energy type battery cells are usually matched for use to prolong the service life, and the application cost is higher.
At present, lead-acid storage batteries are still used in most of high-power application working conditions, but the service life of the lead-acid storage batteries is only 2-3 years, and an effective method for avoiding environmental pollution is still lacking in the aspect of recovery and treatment of the lead-acid storage batteries in the industry.
The sodium ion battery has the unique advantages of rich raw material resources, low cost, environmental friendliness, high energy conversion efficiency, long cycle life, strong power characteristics, good safety and the like, and can be widely applied to various energy storages including a 5G communication base station, a data center, an emergency backup power supply, household energy storage, power grid energy storage and the like. However, the existing sodium ion battery can not meet the requirement of high-rate charge and discharge performance, especially the application of high-power application working condition not lower than 10C.
Disclosure of Invention
The embodiment of the invention provides a sodium ion battery additive and a high-power sodium ion battery, aiming at the problems of short service life and large potential safety hazard of the battery under the existing high-power working condition, and the high-power sodium ion battery additive and the high-power sodium ion battery have high power, high safety and reliability.
In a first aspect, an embodiment of the present invention provides a sodium ion battery additive, where the additive is β -alumina, and a chemical formula of the β -alumina is M 2 O·xAl 2 O 3 Wherein M is I in the periodic Table of the elements A Group elements or I B One or more of group elements, wherein x is 5-11;
the additive is used as an additive of a positive electrode material and/or a negative electrode material of a sodium-ion battery.
Preferably, the I A The group elements include: any one of Li, Na, K and Rb; i is B The group includes Ag.
Preferably, the mass ratio of the additive in the positive electrode material of the sodium-ion battery is 0.1-30%; the mass ratio of the additive in the negative electrode material of the sodium-ion battery is 1-30%.
Preferably, sodium ions in the sodium ion battery migrate within the M-O plane of the beta alumina.
In a second aspect, an embodiment of the present invention provides a high-power sodium ion battery, including: a positive electrode, a negative electrode, a separator and an electrolyte;
wherein the positive electrode includes: the positive electrode comprises a positive electrode material, a positive electrode binder, a positive electrode conductive agent, a positive electrode additive and a positive electrode current collector; the negative electrode includes: the cathode comprises a cathode material, a cathode binder, a cathode conductive agent, a cathode additive and a cathode current collector;
the positive electrode additive and/or the negative electrode additive comprises the sodium ion battery additive of the first aspect.
In the positive electrode, the mass ratio of the positive electrode material is 60-99%, the mass ratio of the positive electrode binder is 0.1-20%, the mass ratio of the positive electrode conductive agent is 0.1-20%, and the mass ratio of the positive electrode additive is 0.1-30%; the single-sided surface density of the positive electrode is 5.0-30.0mg/cm 2 (ii) a The positive current collector is an aluminum foil with the thickness of 4-30 mu m;
the positive electrode material includes: any one of an oxide positive electrode material, a polyanion positive electrode material, a prussian blue positive electrode material, an organic material and a conversion positive electrode material;
wherein the structural general formula of the oxide cathode material is Na x M1O 2 M1 is one or more of transition metal elements;
the structural general formula of the polyanion cathode material is Na x M2 y (X a O b ) z Z w Wherein M2 is one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Ca, Mg, Al, Nb, etc.; x is one or more of Si, S, P, As, B, Mo, W and Ge; z is F or OH;
the structural general formula of the Prussian blue type anode material is A x M a [M b (CN) 6 ] (1-y)·y ·nH 2 O, wherein x is more than or equal to 0 and less than or equal to 2 and 0<y<1, A is an alkali metal ion, M a 、M b Respectively one of Mn and Fe.
Preferably, in the negative electrode, the negative electrode material accounts for 60-99% by mass, the negative electrode binder accounts for 0.1-20% by mass, the negative electrode conductive agent accounts for 0.1-20% by mass, and the negative electrode additive accounts for 1-30% by mass; the single-sided density of the negative electrode is 3.0-20.0mg/cm 2 (ii) a The negative current collector has a thickness of 4-30A μm aluminum or copper foil;
the anode material includes: any one of soft carbon, hard carbon, a composite amorphous carbon material, or lithium titanate.
Preferably, the diaphragm includes: polypropylene, polyethylene, aramid fiber, polyimide or non-woven fabric diaphragm, or ceramic coating diaphragm using the above materials as base materials, or gluing diaphragm; the thickness of the diaphragm is 5-50 μm.
Preferably, the electrolyte is a mixed solution of electrolyte sodium salt and a non-aqueous solvent;
the sodium salt of the electrolyte comprises sodium hexafluorophosphate (NaPF) 6 ) One or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluoroarsenate and sodium chloroaluminate;
the non-aqueous solvent is a mixed solution of chain ester and cyclic ester, wherein the chain ester specifically comprises at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), Methyl Propyl Carbonate (MPC), dipropyl carbonate (DPC) and other chain organic esters containing fluorine, sulfur or unsaturated bonds; the cyclic acid ester specifically includes: at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC), sultone and other cyclic organic esters containing fluorine, sulfur or unsaturated bonds;
the sodium salt concentration of the electrolyte is 0.2-2.0 mol/L.
Preferably, the high-power sodium ion battery is a cylindrical sodium ion battery, a square sodium ion battery or a soft package battery.
The sodium ion battery additive provided by the invention is used as a positive electrode additive and/or a negative electrode additive of a sodium ion battery, so that the internal resistance is effectively reduced, the sodium ion migration performance is improved, and the requirement of 5C-10C multiplying power charge and discharge can be met, wherein the discharge time is more than 3min under the 10C/10C charge and discharge condition; the service life of the charging and discharging cycle at 1C/5C is more than 1000 weeks, and the capacity retention rate is more than 80 percent; the invention realizes the high-rate charge and discharge performance of the cylindrical sodium-ion battery for the first time, particularly the high-rate charge performance, and can meet the charge requirement of not less than 10C.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 is a rate capability test curve of the sodium ion battery provided in example 2 of the present invention at 0.2C-10C;
FIG. 2 is a graph of a rate capability test of the sodium-ion battery of comparative example 1 of the present invention at 0.2C-10C;
fig. 3 is a rapid charge-discharge rate performance test curve of a sodium ion battery provided in embodiment 2 of the present invention under different charge-discharge conditions;
fig. 4 is a rapid charge-discharge rate performance test curve of the sodium ion battery provided in comparative example 1 of the present invention under different charge-discharge conditions.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The invention provides a sodium ion battery additive, which is used for an additive of a positive electrode material and/or a negative electrode material of a sodium ion battery. The additive is beta-alumina, and the chemical formula of the beta-alumina is M 2 O·xAl 2 O 3 Wherein M is I in the periodic Table of the elements A Group elements or I B One or more of group elements, and x is a positive integer; i is A The group elements include: one or more of Li, Na, K or Rb; I.C. A B The group includes Ag and the like.
Taking Na-beta-alumina as an example, the chemical formula is Na 2 O·Al 2 O 3 The crystal structure is characterized in that: the sodium ions are only in a loose plane (Na-O layer) containing equal amounts of sodium ions and oxygen ions, the two Na-O layers are 11.23 angstroms apart, and sandwiched between the Na-O layers are four layers of oxygen atoms; the aluminum ions occupy octahedral positions and tetrahedral positions in the cubic closest packing arrangement, and the close packing base block formed by the four close packing oxygen layers and the aluminum ions is mutually mirror-reflected above and below the Na-O layer.
Due to the above-mentioned Na-beta-aluminaThe Na-O layer is a loose structure of oxygen ions and sodium ions, the distance between Na-O layers is 2.87 angstroms, and normal Na 2 The distance of Na-O in O is 2.4 angstroms, so sodium ions can diffuse in two dimensions in the plane of the Na-O layer.
The mechanism of sodium ion diffusion at the Na — O surface is considered to be that sodium ions occupy interstitial sites between ions, and diffusion is effected by ionic transition from the interstitial sites to normal sites. Therefore, the migration of sodium ions in the M-O plane of the beta-alumina is effectively enhanced, so that the internal resistance is reduced, and the migration performance of the sodium ions is improved.
The additive is applied to a high-power sodium-ion battery. The high power sodium ion battery includes: a positive electrode, a negative electrode, a separator, and an electrolyte.
Wherein the positive electrode includes: the positive electrode comprises a positive electrode material, a positive electrode binder, a positive electrode conductive agent, a positive electrode additive and a positive electrode current collector; the negative electrode includes: the cathode comprises a cathode material, a cathode binder, a cathode conductive agent, a cathode additive and a cathode current collector; the positive electrode additive and/or the negative electrode additive comprises the sodium ion battery additive.
In the positive electrode, the mass ratio of the positive electrode material is 60-99%, the mass ratio of the positive electrode binder is 0.1-20%, the mass ratio of the positive electrode conductive agent is 0.1-20%, and the mass ratio of the positive electrode additive is 0.1-30%; the single-sided surface density of the positive electrode is 5.0-30.0mg/cm 2 (ii) a The positive current collector is an aluminum foil with the thickness of 4-30 mu m;
the positive electrode material includes: any one of an oxide positive electrode material, a polyanion positive electrode material, a prussian blue positive electrode material, an organic material and a conversion positive electrode material;
wherein, the structural general formula of the oxide anode material is Na x M1O 2 M1 is one or more of transition metal elements, such as a ferro manganese copper-based positive electrode material or a ferro manganese copper-based positive electrode material; the structural general formula of the polyanion cathode material is Na x M2 y (X a O b ) z Z w Wherein M2 is one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Ca, Mg, Al, Nb, etc.; x is one of Si, S, P, As, B, Mo, W and GeOne or more of the above-mentioned raw materials; z is F or OH; the structural general formula of the Prussian blue type anode material is A x M a [M b (CN) 6 ] (1-y)·y ·nH 2 O, wherein x is more than or equal to 0 and less than or equal to 2 and 0<y<1, A is an alkali metal ion, M a 、M b Respectively one of Mn and Fe.
In the negative electrode, the mass ratio of the negative electrode material is 60-99%, the mass ratio of the negative electrode binder is 0.1-20%, the mass ratio of the negative electrode conductive agent is 0.1-20%, and the mass ratio of the negative electrode additive is 1-30%; the single-sided density of the negative electrode is 3.0-20.0mg/cm 2 (ii) a The negative current collector is an aluminum foil or a copper foil with the thickness of 4-30 mu m; the anode material includes: any one of soft carbon, hard carbon, a composite amorphous carbon material, or lithium titanate.
The diaphragm includes: polypropylene, polyethylene, aramid fiber, polyimide or non-woven fabric diaphragm, or ceramic coating diaphragm using the above materials as base materials, or gluing diaphragm; the thickness of the separator is 5 to 50 μm.
The electrolyte is a mixed solution of electrolyte sodium salt and a non-aqueous solvent; the sodium salt of the electrolyte comprises sodium hexafluorophosphate (NaPF) 6 ) One or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluoroarsenate and sodium chloroaluminate; the non-aqueous solvent is a mixed solution of chain ester and cyclic acid ester, wherein the chain ester specifically comprises at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Methyl Propyl Carbonate (MPC), dipropyl carbonate (DPC) and other chain organic esters containing fluorine, sulfur or unsaturated bonds; the cyclic acid ester specifically includes: at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC), sultone and other cyclic organic esters containing fluorine, sulfur or unsaturated bonds; the concentration of sodium salt of the electrolyte is 0.2-2.0 mol/L.
The high-power sodium ion battery can be a cylindrical sodium ion battery, a square sodium ion battery or a soft package battery.
In order to better understand the technical scheme provided by the invention, the following specific examples are respectively further explained.
Example 1
Preparing a positive pole piece: adding 100 wt% of solvent N-methyl pyrrolidone (NMP) and 5 wt% of adhesive polyvinylidene fluoride (PVDF) powder into a planetary stirring cylinder, stirring for 2 hours at the speed of revolution of 30r/min and dispersion of 3000r/min, then adding 5 wt% of conductive agent carbon black (SP), stirring for 1 hour at the speed of revolution of 30r/min and dispersion of 3000r/min, then adding 5 wt% of Na-beta-alumina, stirring for 1 hour at the speed of revolution of 30r/min and dispersion of 3000r/min, then adding 85 wt% of positive electrode active material O3-Na [ Cu ] Cu 0.22 Fe 0.3 Mn 0.48 ]O 2 Stirring for 3 hours according to revolution of 30r/min and dispersion of 3000r/min, defoaming, and sieving by a 200-mesh sieve to finish the preparation of the positive electrode slurry of the sodium-ion battery;
and uniformly coating the prepared anode slurry on an aluminum foil with the thickness of 15 mu m in an extrusion mode, and drying, rolling and slitting to prepare the anode piece.
Preparing a negative pole piece: adding 100 wt% of deionized water and 5 wt% of adhesive polyvinylidene fluoride (PVDF) powder into a planetary stirring cylinder, stirring for 2 hours at the speed of revolution of 30r/min and dispersion of 3000r/min, then adding 5 wt% of SP, stirring for 1 hour at the speed of revolution of 30r/min and dispersion of 3000r/min, then adding 5 wt% of Na-beta-alumina, stirring for 1 hour at the speed of revolution of 30r/min and dispersion of 3000r/min, then adding 85 wt% of hard carbon material of anthracite as a negative electrode active substance, stirring for 3 hours at the speed of revolution of 30r/min and dispersion of 3000r/min, defoaming, and then sieving with a 200-mesh sieve to complete the preparation of the negative electrode slurry of the sodium ion battery;
and uniformly coating the prepared cathode slurry on an aluminum foil with the thickness of 15 mu m in an extrusion mode, and drying, rolling and slitting to prepare the cathode pole piece.
And (3) preparing the obtained positive and negative electrode sheets, winding a PE diaphragm coated by 12um +4um alumina ceramic, assembling and baking, injecting 12 g/piece of electrolyte, wherein the concentration of sodium hexafluorophosphate is 1mol/L, and the solvent is Ethylene Carbonate (EC): diethyl carbonate (DEC): propylene Carbonate (PC) ═ 1: 1: the electrolyte of 1 is subjected to the processes of formation, aging, capacity grading and the like after being injected with liquid, and the 26650 battery cell is prepared and finished, and is numbered A1.
Example 2
A26650 cell was prepared in the same manner as in example 1, except that in the positive and negative electrode materials, Na-. beta. -alumina was 10 wt%, the positive and negative electrode active materials were 80 wt%, and the material was numbered A2.
Example 3
A26650 cell was prepared in the same manner as in example 1, except that in the positive and negative electrode materials, Na-. beta. -alumina was 15 wt%, the positive and negative electrode active materials were 75 wt%, and the material was numbered A3.
Example 4
26650 cells were prepared by the same method as in example 1, except that the positive and negative electrode materials contained 20 wt% of Na- β -alumina, 70 wt% of the positive and negative electrode active materials, and No. a 4.
Example 5
26650 cells were prepared by the same method as in example 1, except that in the positive and negative electrode materials, Na — β -alumina was 25 wt%, the positive and negative electrode active materials were 65 wt%, and the number was a 5.
Example 6
26650 cells were prepared by the same method as in example 1, except that in the positive and negative electrode materials, Na — β -alumina was 30 wt%, the positive and negative electrode active materials were 60 wt%, and the number was a 6.
Comparative example 1
26650 cells were prepared in the same manner as in example 1, except that no Na- β -alumina was added to the positive and negative electrode slurry, the proportion of positive and negative electrode active materials was 90%, and No. B1 was used in example 1.
And (3) carrying out electrochemical performance test on the assembled battery by adopting a constant-current and constant-voltage charging mode and a constant-current discharging mode, wherein the cut-off voltage range of charging and discharging is 1.5-4V. The temperature is 25 ℃ at room temperature, and the tested charge and discharge currents are 0.2C, 1C, 3C, 5C, 8C and 10C. The test results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the retention rates of the A1-A6 and 0.2C/10C discharge capacities obtained in the examples are all larger than that of the B1 obtained in the comparative example, which shows that the invention has obvious improvement effect on the rate capability of the battery cell,
as can be seen from the data in Table 1 in example 2 and comparative example 1, the weight ratio of Na-beta-alumina is 10%, and the rate capability is obviously improved
FIG. 1 is a rate performance test curve of a sodium ion battery provided in example 2 of the present invention at 0.2C-10C; FIG. 2 is a rate performance test curve of the sodium-ion battery provided in comparative example 1 at 0.2C-10C; as can be seen by comparison, the 10C discharge capacity in example 2 is significantly greater than that in comparative example 1, increasing the rate by 5.1%.
Fig. 3 is a rapid charge-discharge rate performance test curve of the sodium ion battery provided in embodiment 2 of the present invention under different charge-discharge conditions; fig. 4 is a curve of rapid charge and discharge rate performance test of the sodium ion battery provided in comparative example 1 under different charge and discharge conditions, and it can be seen by comparison that, during high-rate charge and discharge, the tests in example 2 are ahead of those in comparative example 1, and the difference is more obvious when the rate is larger, and especially when the sodium ion battery is charged and discharged at a rate of 10C/10C, the discharge retention rate of comparative example 2 is increased to 50% from 12.5% compared with that of comparative example 1; the high-current charging capability is obviously improved.
The sodium ion battery additive provided by the invention is used as a positive electrode additive and/or a negative electrode additive of a sodium ion battery, so that the internal resistance is effectively reduced, the sodium ion migration performance is improved, and the requirement of 5C-10C multiplying power charge and discharge can be met, wherein the discharge time is more than 3min under the 10C/10C charge and discharge condition; the service life of the charging and discharging cycle at 1C/5C is more than 1000 weeks, and the capacity retention rate is more than 80 percent; the invention realizes the high-rate charge and discharge performance of the cylindrical sodium ion battery for the first time, particularly the high-rate charge performance, and can meet the charge requirement of not less than 10C.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The sodium-ion battery additive is characterized in that the additive is beta-alumina, and the chemical formula of the beta-alumina is M 2 O·xAl 2 O 3 Wherein M is I in the periodic table A Group elements or I B One or more of group elements, wherein x is 5-11;
the additive is used as an additive of a positive electrode material and/or a negative electrode material of a sodium-ion battery.
2. The sodium ion battery additive of claim 1, wherein I is A The group elements include: any one of Li, Na, K and Rb; i is B The group includes Ag.
3. The sodium-ion battery additive according to claim 1, wherein the mass ratio of the additive in the positive electrode material of the sodium-ion battery is 0.1-30%; the mass ratio of the additive in the negative electrode material of the sodium-ion battery is 1-30%.
4. The sodium ion battery additive according to claim 1, wherein sodium ions in the sodium ion battery migrate within the M-O plane of the beta alumina.
5. A high power sodium ion battery, comprising: a positive electrode, a negative electrode, a separator and an electrolyte;
wherein the positive electrode includes: the cathode comprises a cathode material, a cathode binder, a cathode conductive agent, a cathode additive and a cathode current collector; the negative electrode includes: the cathode comprises a cathode material, a cathode binder, a cathode conductive agent, a cathode additive and a cathode current collector;
the positive electrode additive and/or negative electrode additive comprises the sodium ion battery additive of claim 1.
6. The high-power sodium-ion battery according to claim 5, wherein in the positive electrode, the positive electrode material accounts for 60-99% by mass, the positive electrode binder accounts for 0.1-20% by mass, the positive electrode conductive agent accounts for 0.1-20% by mass, and the positive electrode additive accounts for 0.1-30% by mass; the single-sided surface density of the positive electrode is 5.0-30.0mg/cm 2 (ii) a The positive current collector is an aluminum foil with the thickness of 4-30 mu m;
the positive electrode material includes: any one of an oxide positive electrode material, a polyanion positive electrode material, a prussian blue positive electrode material, an organic material and a conversion positive electrode material;
wherein the structural general formula of the oxide cathode material is Na x M1O 2 M1 is one or more of transition metal elements;
the structural general formula of the polyanion cathode material is Na x M2 y (X a O b ) z Z w Wherein M2 is one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Ca, Mg, Al, Nb, etc.; x is one or more of Si, S, P, As, B, Mo, W and Ge; z is F or OH;
the structural general formula of the Prussian blue type anode material is A x M a [M b (CN) 6 ] (1-y)·y ·nH 2 O, wherein x is more than or equal to 0 and less than or equal to 2 and 0<y<1, A is an alkali metal ion, M a 、M b Respectively one of Mn and Fe.
7. The high-power sodium-ion battery according to claim 5, wherein in the negative electrode, the negative electrode material accounts for 60-99% by mass, the negative electrode binder accounts for 0.1-20% by mass, the negative electrode conductive agent accounts for 0.1-20% by mass, and the negative electrode additive accounts for 1-30% by mass; the single-sided density of the negative electrode is 3.0-20.0mg/cm 2 (ii) a The negative current collector is an aluminum foil or a copper foil with the thickness of 4-30 mu m;
the anode material includes: any one of soft carbon, hard carbon, a composite amorphous carbon material, or lithium titanate.
8. The high power sodium ion battery of claim 5, wherein the separator comprises: polypropylene, polyethylene, aramid fiber, polyimide or non-woven fabric diaphragm, or ceramic coating diaphragm using the above materials as base materials, or gluing diaphragm; the thickness of the diaphragm is 5-50 μm.
9. The high power sodium ion battery of claim 5, wherein the electrolyte is a mixed solution of electrolyte sodium salt and non-aqueous solvent;
the sodium salt of the electrolyte comprises sodium hexafluorophosphate (NaPF) 6 ) One or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluoroarsenate and sodium chloroaluminate;
the non-aqueous solvent is a mixed solution of chain ester and cyclic ester, wherein the chain ester specifically comprises at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), Methyl Propyl Carbonate (MPC), dipropyl carbonate (DPC) and other chain organic esters containing fluorine, sulfur or unsaturated bonds; the cyclic acid ester specifically includes: at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC), sultone and other cyclic organic esters containing fluorine, sulfur or unsaturated bonds;
the sodium salt concentration of the electrolyte is 0.2-2.0 mol/L.
10. The high power sodium ion battery of claim 5, wherein the high power sodium ion battery is a cylindrical sodium ion battery, a prismatic sodium ion battery, or a pouch battery.
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