CN114843450A - Sodium ion battery - Google Patents
Sodium ion battery Download PDFInfo
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- CN114843450A CN114843450A CN202210692882.7A CN202210692882A CN114843450A CN 114843450 A CN114843450 A CN 114843450A CN 202210692882 A CN202210692882 A CN 202210692882A CN 114843450 A CN114843450 A CN 114843450A
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- China
- Prior art keywords
- sodium
- negative electrode
- ion battery
- active material
- electrolytic solution
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 42
- 239000007773 negative electrode material Substances 0.000 claims abstract description 44
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 28
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 210000003918 fraction a Anatomy 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims description 25
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 20
- 229910021385 hard carbon Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 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 11
- 239000007774 positive electrode material Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 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
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920000447 polyanionic polymer Polymers 0.000 claims description 2
- 229960003351 prussian blue Drugs 0.000 claims description 2
- 239000013225 prussian blue Substances 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 239000006258 conductive agent Substances 0.000 description 19
- 239000011883 electrode binding agent Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 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
- 230000003247 decreasing effect Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M10/05—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of secondary batteries, and particularly provides a sodium ion battery. The sodium ion battery comprises a positive electrode, a negative electrode and a non-aqueous electrolyte; the negative electrode contains a negative electrode active material, and the mass fraction a of the negative electrode active material in the negative electrode, the specific surface area b of the negative electrode active material, the density x of the nonaqueous electrolytic solution, and the molar conductivity y of the nonaqueous electrolytic solution satisfy 0.3. ltoreq. a x b x/y. ltoreq.1.5. The invention creatively designs the electrolyte from multiple aspects of comprehensive consideration of the mass fraction a of the negative active material in the negative electrode, the specific surface area b of the negative active material, the density x of the non-aqueous electrolyte and the molar conductivity y, and can effectively reduce the internal resistance of the sodium-ion battery and increase the battery capacity, so that the sodium-ion battery has the advantages of low internal resistance, good cycling stability and the like.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a sodium ion battery.
Background
The cost of lithium ion batteries is greatly increased due to the limited global reserve of lithium resources. The abundance of sodium resources is high, the material cost is low, and the functions similar to those of the lithium ion battery can be realized technically, so that the development of the high-performance sodium ion battery is beneficial to relieving the resource problem of the new energy industry. Unlike the graphite negative electrode of the lithium ion battery, the negative electrode of the sodium ion battery generally uses an amorphous carbon material with a larger comparative area as the negative electrode, such as hard carbon, and since the larger the specific surface area of the electrode active material is, the more the electrolyte is consumed in the battery, the electrolyte design of the sodium ion battery is greatly different from that of the lithium ion battery.
The sodium ion battery uses amorphous carbon with a large specific surface area as a negative electrode, consumes more electrolyte in the battery formation stage, and has thick film formation, so that the battery has high internal resistance and low battery capacity.
Disclosure of Invention
Based on this, the invention aims to provide a sodium ion battery which has the advantages of low internal resistance, good cycling stability and the like.
In order to achieve the purpose, the invention adopts the following technical scheme.
A sodium-ion battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolytic solution; the negative electrode contains a negative electrode active material, and the mass fraction a of the negative electrode active material in the negative electrode, the specific surface area b of the negative electrode active material, the density x of the nonaqueous electrolytic solution, and the molar conductivity y of the nonaqueous electrolytic solution satisfy 0.3. ltoreq. a x b x/y. ltoreq.1.5.
In some embodiments, the a, b, x, and y satisfy 0.4 ≦ a × b × x/y ≦ 1.3.
In some embodiments, the mass fraction a of the negative active material in the negative electrode is 90% to 99%.
In some embodiments, the negative active material has a specific surface area b of 3 to 7g/m 2 。
In some embodiments, the density x of the nonaqueous electrolyte solution is 0.8-1.4 g/cm 3 . Preferably, the density x of the nonaqueous electrolytic solution is 0.9 to 1.3g/cm 3 。
In some embodiments, the molar conductivity y of the nonaqueous electrolyte is 5 to 12S-cm 2 And/mol. Preferably, the molar conductivity y of the nonaqueous electrolytic solution is 6 to 11S-cm 2 /mol。
In some embodiments, the negative active material is selected from at least one of hard carbon, soft carbon, graphite, graphene, mesocarbon microbeads.
In some embodiments, the nonaqueous electrolyte contains an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt is selected from at least one of sodium hexafluorophosphate, sodium bistrifluoromethanesulfonimide, sodium bifluorosulfonimide, sodium perchlorate, sodium triflate, and sodium tetrafluoroborate.
In some embodiments, the solvent is selected from at least one of a carbonate of C3 to C5, a carboxylate of C2 to C6, and an ether of C4 to C10.
In some embodiments, the positive electrode includes a positive electrode active material selected from at least one of a sodium-containing layered oxide, a sodium-containing polyanion compound, and a sodium-containing prussian blue compound.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the problems of large internal resistance and low battery capacity of the sodium-ion battery, the invention creatively provides a sodium-ion battery which is designed by comprehensively considering the mass fraction a of a negative electrode active material in the negative electrode, the specific surface area b of the negative electrode active material, the density x of a nonaqueous electrolytic solution and the molar conductivity y of the nonaqueous electrolytic solution in multiple aspects: for the carbon negative electrode with larger specific surface area, the density of the non-aqueous electrolyte is reduced, the content of the non-aqueous electrolyte absorbed by the unit volume of the negative electrode can be reduced, and the non-aqueous electrolyte consumed by side reaction in the film forming process is reduced; the molar conductivity of the non-aqueous electrolyte is increased, so that the carrier utilization rate in the film forming process is improved, anions are reduced to participate in film forming, and a thinner interface film is formed. And further research shows that when the mass fraction a of the negative electrode active material in the negative electrode, the specific surface area b of the negative electrode active material, the density x of the nonaqueous electrolyte and the molar conductivity y of the nonaqueous electrolyte meet 0.3-1.5, the internal resistance of the sodium-ion battery can be effectively reduced, and the battery capacity can be increased, so that the sodium-ion battery has the advantages of low internal resistance, good cycle stability and the like.
Detailed Description
Experimental procedures according to the invention, in which no particular conditions are specified in the following examples, are generally carried out under conventional conditions, or under conditions recommended by the manufacturer. The various chemicals used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The present embodiment provides a sodium-ion battery including a positive electrode, a negative electrode, and a nonaqueous electrolytic solution; the negative electrode contains a negative electrode active material, and the mass fraction a of the negative electrode active material in the negative electrode, the specific surface area b of the negative electrode active material, the density x of the nonaqueous electrolytic solution, and the molar conductivity y of the nonaqueous electrolytic solution satisfy 0.3. ltoreq. a x b x/y. ltoreq.1.5.
The inventor finds that when the value of a multiplied by b multiplied by x/y is higher than 1.5, the unit volume of the negative electrode adsorbs more electrolyte, and the electrolyte consumes more electrolyte; the molar conductivity is lower, the film forming kinetic process is slower, more anions participate in film forming, and the formed interface film is thicker, so that the internal resistance of the battery is higher; when the value of a x b x/y is less than 0.3, the amount of electrolyte absorbed per unit volume of the negative electrode is too small, and the film formation is insufficient, resulting in the formation of an unstable interface film; the electrolyte has high molar conductivity, a film forming kinetic process is fast, anions participate in film forming less, the mechanical strength of an interface film is unstable, and the battery cycling stability is reduced.
In some preferred embodiments, the a, b, x, and y satisfy 0.4. ltoreq. a x b x/y. ltoreq.1.3.
Specifically, the value of a × b × x/y is 0.25, 0.28, 0.3, 0.4, 0.43, 0.45, 0.5, 0.65, 0.75, 0.8, 0.82, 0.9, 0.98, 1, 1.2, 1.25, 1.3, 1.4, 1.5, 1.65, 1.86.
In some embodiments, the mass fraction a of the negative active material in the negative electrode is 90% to 99%.
In some embodiments, the negative active material has a specific surface area b of 3 to 7g/m 2 。
In some embodiments, the density x of the nonaqueous electrolyte solution is 0.8-1.4 g/cm 3 。
In some preferred embodiments, the density x of the nonaqueous electrolytic solution is 0.9-1.3 g/cm 3 。
In some embodiments, the molar conductivity y of the nonaqueous electrolyte is 5 to 12S-cm 2 /mol。
In some preferred embodiments, the molar conductivity y of the nonaqueous electrolytic solution is 6 to 11S-cm 2 /mol。
In some embodiments, the negative active material is selected from at least one of hard carbon, soft carbon, graphite, graphene, mesocarbon microbeads.
In some embodiments, the nonaqueous electrolyte contains an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt is selected from at least one of sodium hexafluorophosphate, sodium bistrifluoromethanesulfonimide, sodium bifluorosulfonimide, sodium perchlorate, sodium triflate, and sodium tetrafluoroborate.
In some embodiments, the solvent is selected from at least one of a carbonate of C3 to C5, a carboxylate of C2 to C6, and an ether of C4 to C10.
In some preferred embodiments, the solvent is selected from at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, ethyl propionate, propyl propionate, γ -butyrolactone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether.
In some embodiments, the positive electrode comprises a positive active material including, but not limited to, at least one of a transition metal oxide, a prussian-type material, a phosphate, a sulfate, a titanate material. Wherein the transition metal oxide may have a chemical formula of Na z M x O y M is at least one selected from Cr, Fe, Co, Ni, Cu, Mn, Sn, Mo, Sb and V, and more preferably, the transition metal oxide is NaNi m Fe n Mn p O 2 (m + n + p is 1, m is 0. ltoreq. 1, n is 0. ltoreq. 1, p is 0. ltoreq. 1) or NaNi m Co n Mn p O 2 (m + n + p is 1, m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and p is more than or equal to 0 and less than or equal to 1); the molecular formula of the prussian material is Na x M[M′(CN) 6 ] y ·zH 2 O, wherein M is a transition metal, M' is a transition metal, 0<x≤2，0.8≤y<1，0<z is less than or equal to 20, and more preferably, the prussian material is Na x Mn[Fe(CN) 6 ] y ·nH 2 O (x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, and z is more than 0 and less than or equal to 10) or Na x Fe[Fe(CN) 6 ] y ·nH 2 O (x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, and z is more than 0 and less than or equal to 10); the chemical formula of the phosphate is Na 3 (MO 1- x PO 4 ) 2 F 1+2x X is more than or equal to 0 and less than or equal to 1, M is at least one selected from Al, V, Ge, Fe and Ga, and more preferably, the phosphate is Na 3 (VPO 4 ) 2 F 3 Or Na 3 (VOPO 4 ) 2 F; the chemical formula of the phosphate is Na 2 MPO 4 F and M are selected from at least one of Fe and Mn, more preferably, the phosphate is Na 2 FePO 4 F or Na 2 MnPO 4 F; the titanate material may be selected from Na 2 Ti 3 O 7 、Na 2 Ti 6 O 13 、Na 4 Ti 5 O 12 、Li 4 Ti 5 O 12 、NaTi 2 (PO 4 ) 3 At least one of; the chemical formula of the sulfate is Na 2 M(SO 4 ) 2 ·2H 2 O and M are at least one selected from Cr, Fe, Co, Ni, Cu, Mn, Sn, Mo, Sb and V.
In some embodiments, the positive electrode further comprises a positive electrode binder and a positive electrode conductive agent.
The positive binder comprises thermoplastic resins such as polyvinylidene fluoride, copolymers of vinylidene fluoride, polytetrafluoroethylene, copolymers of vinylidene fluoride and hexafluoropropylene, copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether, copolymers of ethylene and tetrafluoroethylene, copolymers of vinylidene fluoride and trifluoroethylene, copolymers of vinylidene fluoride and trichloroethylene, copolymers of vinylidene fluoride and fluoroethylene, copolymers of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene, thermoplastic polyimide, polyethylene, polypropylene and the like; an acrylic resin; and styrene butadiene rubber.
The positive electrode conductive agent comprises at least one of conductive carbon black, conductive carbon spheres, conductive graphite, conductive carbon fibers, carbon nanotubes, graphene or reduced graphene oxide.
In some embodiments, the negative electrode further comprises a negative electrode binder and a negative electrode conductive agent. The negative electrode binder and the negative electrode conductive agent may be the same as the positive electrode binder and the positive electrode conductive agent, respectively, and are not described herein again.
In some embodiments, the method of preparing the positive electrode is: and uniformly mixing the positive electrode active material, the positive electrode binder, the positive electrode conductive agent and the positive electrode solvent, coating the mixture on a base material, and removing the positive electrode solvent to obtain the positive electrode. The positive electrode solvent is of conventional choice and may be, for example, a Nitrogen Methyl Pyrrolidinone (NMP).
In some embodiments, the method of preparing the negative electrode is: and uniformly mixing the negative electrode active material, the negative electrode binder, the negative electrode conductive agent and the negative electrode solvent, coating the mixture on a base material, and removing the negative electrode solvent to obtain the negative electrode. The negative electrode solvent is a conventional choice and may be, for example, pure water.
In some embodiments, a separator is also included in the sodium-ion battery, the separator being positioned between the positive electrode and the negative electrode.
The diaphragm can be an existing conventional diaphragm, and can be a ceramic diaphragm, a polymer diaphragm, non-woven fabric, an inorganic-organic composite diaphragm and the like, including but not limited to diaphragms such as single-layer PP (polypropylene), single-layer PE (polyethylene), double-layer PP/PE, double-layer PP/PP and three-layer PP/PE/PP.
In some embodiments, the preparation method of the sodium-ion battery is a general preparation method of a secondary battery, namely, a positive electrode, a separator and a negative electrode are combined and a nonaqueous electrolyte is injected to obtain the sodium-ion battery.
The following description will be given with reference to specific examples.
Example 1
The present embodiment provides a sodium ion battery including a positive electrode, a negative electrode, and a nonaqueous electrolytic solution.
The preparation method of the non-aqueous electrolyte comprises the following steps: ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate are mixed according to the mass ratio of 25: 10: 30: 35 preparing a mixed solvent, preparing 100g of the mixed solvent and 14g of sodium hexafluorophosphate into a solution, and obtaining a solution with the density x of 1.2g/cm 3 The molar conductivity y is 7S cm 2 Solution per mol.
The negative electrode comprises a negative electrode active material, a negative electrode binder and a negative electrode conductive agent; the negative electrode active material is hard carbon, the mass fraction a of the hard carbon in the negative electrode is 95%, and the specific surface area b of the hard carbon is 6g/m 2 (ii) a The mass fraction of the negative electrode binder in the negative electrode is 3%; the mass fraction of the negative electrode conductive agent in the negative electrode is 2%.
The positive electrode comprises a positive active material, a positive binder and a positive conductive agent; the positive active material is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (ii) a The mass ratio of the positive electrode active material to the positive electrode binder to the positive electrode conductive agent is 96: 2: 2.
in this embodiment, the value of a × b × x/y is 0.98.
Example 2
The present embodiment provides a sodium ion battery including a positive electrode, a negative electrode, and a nonaqueous electrolytic solution.
The preparation method of the non-aqueous electrolyte comprises the following steps: ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate are mixed according to the mass ratio of 25: 10: 30: 35 preparing a mixed solvent, preparing 100g of the mixed solvent and 14.7g of sodium hexafluorophosphate into a solution, and obtaining a density x of 1.2g/cm 3 The molar conductivity y was 6.5 S.cm 2 Solution per mol.
The negative electrode comprises a negative electrode active material, a negative electrode binder and a negative electrode conductive agent; the negative electrode active material is hard carbon, the mass fraction a of the hard carbon in the negative electrode is 97%, and the specific surface area b of the hard carbon is 7g/m 2 (ii) a The mass fraction of the negative electrode binder in the negative electrode is 2%; the mass fraction of the negative electrode conductive agent in the negative electrode is 1%.
The positive electrode was the same as in example 1.
In this example, the value of a × b × x/y is 1.25.
Example 3
The present embodiment provides a sodium ion battery including a positive electrode, a negative electrode, and a nonaqueous electrolytic solution.
The preparation method of the non-aqueous electrolyte comprises the following steps: ethylene carbonate, propylene carbonate, diethyl carbonate and ethyl methyl carbonate are mixed according to the mass ratio of 20: 10: 60: 10 preparing a mixed solvent, preparing 100g of the mixed solvent and 9.5g of sodium hexafluorophosphate into a solution, and obtaining a density x of 1.1g/cm 3 The molar conductivity y was 9.5 S.cm 2 Solution per mol.
The negative electrode comprises a negative electrode active material, a negative electrode binder and a negative electrode conductive agent; the negative electrode active material is hard carbon, the mass fraction a of the hard carbon in the negative electrode is 93%, and the specific surface area b of the hard carbon is 4g/m 2 (ii) a The mass fraction of the negative electrode binder in the negative electrode is 4%; the mass fraction of the negative electrode conductive agent in the negative electrode is 3%.
The positive electrode was the same as in example 1.
In this embodiment, the value of a × b × x/y is 0.43.
Comparative example 1:
the present comparative example provides a sodium-ion battery including a positive electrode, a negative electrode, and a nonaqueous electrolytic solution.
The preparation method of the non-aqueous electrolyte comprises the following steps: mixing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate according to a mass ratio of 80: 5: 15 preparing a mixed solvent, preparing 100g of the mixed solvent and 21.8g of sodium hexafluorophosphate into a solution, and obtaining a solution with the density x of 1.4g/cm 3 The molar conductivity y is 5S cm 2 Solution per mol.
The negative electrode comprises a negative electrode active material, a negative electrode binder and a negative electrode conductive agent; the negative electrode active material is hard carbon, the mass fraction a of the hard carbon in the negative electrode is 95%, and the specific surface area b of the hard carbon is 7g/m 2 (ii) a The mass fraction of the negative electrode binder in the negative electrode is 3%; the mass fraction of the negative electrode conductive agent in the negative electrode is 2%.
The positive electrode was the same as in example 1.
The value of a x b x y in this comparative example is 1.86.
Comparative example 2:
the present comparative example provides a sodium-ion battery including a positive electrode, a negative electrode, and a nonaqueous electrolytic solution.
The preparation method of the non-aqueous electrolyte comprises the following steps: propylene carbonate, diethyl carbonate and propyl propionate are mixed according to the mass ratio of 10: 5: 85 to obtain a mixed solvent, and mixing 100g of the mixed solvent with 4g of sodium hexafluorophosphate to obtain a solution with a density x of 0.9g/cm 3 The molar conductivity y is 12S cm 2 Solution per mol.
The negative electrode comprises a negative electrode active material, a negative electrode binder and a negative electrode conductive agent; the negative electrode active material is hard carbon, the mass fraction a of the hard carbon in the negative electrode is 93%, and the specific surface area b of the hard carbon is 4g/m 2 (ii) a The mass fraction of the negative electrode binder in the negative electrode is 4%; the mass fraction of the negative electrode conductive agent in the negative electrode is 3%.
The positive electrode was the same as in example 1.
The value of a x b x y in this comparative example is 0.28.
The performance of the sodium ion batteries of examples 1 to 3 and comparative examples 1 to 2 was tested: and carrying out a cyclic charge-discharge test in a voltage range of 1.50-3.95V, and recording the internal resistance of the battery and the capacity retention rate after 200 cycles.
The results are shown in table 1:
table 1 results of performance testing
The results show that the sodium ion battery has lower internal resistance, higher capacity retention rate and better battery performance.
Compared with example 1, the negative electrode active material used in the sodium ion battery of comparative example 1 has higher specific surface area, higher density of the non-aqueous electrolyte, lower molar conductivity, a x b x/y value of 1.86 which is more than 1.50, more electrolyte adsorbed in unit volume of the negative electrode, and more consumption of the non-aqueous electrolyte; the molar conductivity is lower, the film forming kinetic process is slower, more anions participate in film forming, and the formed interface film is thicker, so that the internal resistance of the battery is higher.
The negative electrode active material used in comparative example 2 had a lower specific surface area, a lower density of the nonaqueous electrolyte, a higher molar conductivity, an a × b × x/y value of 0.28 and less than 0.30, and an unstable interface film formed due to insufficient film formation due to too little nonaqueous electrolyte adsorbed per unit volume of the negative electrode, as compared with example 1; the nonaqueous electrolyte has high molar conductivity, a film forming kinetic process is fast, anions participate in film forming less, the mechanical strength of an interface film is unstable, the battery cycle stability is reduced, and the battery capacity retention rate is low.
Example 2 compares with comparative example 1, when a negative active material having a higher specific surface area is used, the value of x is decreased, and the value of y is increased so that a, b, x, and y satisfy 0.3. ltoreq. a.xbxx/y. ltoreq.1.5, and lower impedance can be obtained.
Example 3 compares with comparative example 2, when the negative active material with lower specific surface area is used, the value of x is increased, the value of y is decreased, and a, b, x and y satisfy 0.3 ≤ a × b × x/y ≤ 1.5, and better cycle performance can be obtained.
In summary, the invention optimizes the mass fraction a of the negative electrode active material in the sodium-ion battery, the specific surface area b of the negative electrode active material, the density x of the nonaqueous electrolyte and the molar conductivity y of the nonaqueous electrolyte so that a, b, x and y satisfy 0.3-1.5 of a multiplied by b multiplied by x/y, thereby effectively improving the cycle stability of the sodium-ion battery and reducing the internal resistance of the battery. When the value of a x b x/y is not within the range of the present invention, the performance of the sodium-ion battery obtained by the preparation is significantly reduced.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A sodium-ion battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolytic solution; the negative electrode contains a negative electrode active material, and the mass fraction a of the negative electrode active material in the negative electrode, the specific surface area b of the negative electrode active material, the density x of the nonaqueous electrolytic solution, and the molar conductivity y of the nonaqueous electrolytic solution satisfy 0.3. ltoreq. a.ltoreq.b.xx/y.ltoreq.1.5.
2. The sodium ion battery of claim 1, wherein a, b, x, and y satisfy 0.4 ≦ a x b x/y ≦ 1.3.
3. The sodium-ion battery of claim 1, wherein the mass fraction a of the negative active material in the negative electrode is 90% to 99%.
4. The sodium-ion battery according to claim 1, wherein the negative active material has a specific surface area b of 3 to 7g/m 2 。
5. The sodium-ion battery according to claim 1, wherein the density x of the nonaqueous electrolytic solution is 0.8 to 1.4g/cm 3 。
6. The sodium-ion battery according to claim 1, wherein the molar conductivity y of the nonaqueous electrolytic solution is 5 to 12S-cm 2 /mol。
7. The sodium ion battery of claim 1, wherein the negative active material is selected from at least one of hard carbon, soft carbon, graphite, graphene, mesocarbon microbeads.
8. The sodium-ion battery of claim 1, wherein the nonaqueous electrolyte contains an electrolyte salt and a solvent.
9. The sodium ion battery of claim 8, wherein the electrolyte salt is selected from at least one of sodium hexafluorophosphate, sodium bistrifluoromethanesulfonylimide, sodium bifluorosulfonylimide, sodium perchlorate, sodium triflate, and sodium tetrafluoroborate; and/or the solvent is at least one selected from carbonate of C3-C5, carboxylate of C2-C6 and ether of C4-C10.
10. The sodium-ion battery according to any one of claims 1 to 9, wherein the positive electrode comprises a positive electrode active material selected from at least one of a sodium-containing layered oxide, a sodium-containing polyanion compound, and a sodium-containing prussian blue compound.
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| WO2023241299A1 (en) * | 2022-06-17 | 2023-12-21 | 深圳新宙邦科技股份有限公司 | Sodium ion battery |
| WO2024046110A1 (en) * | 2022-09-02 | 2024-03-07 | 深圳新宙邦科技股份有限公司 | Sodium-ion secondary battery |
| WO2024125096A1 (en) * | 2022-12-12 | 2024-06-20 | 深圳新宙邦科技股份有限公司 | Sodium-ion secondary battery |
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| CN114843450A (en) * | 2022-06-17 | 2022-08-02 | 深圳新宙邦科技股份有限公司 | Sodium ion battery |
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| CN105580184A (en) * | 2013-09-25 | 2016-05-11 | 国立大学法人东京大学 | Non-aqueous electrolyte secondary battery |
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