CN115842112A - Secondary battery, battery module, battery pack, and electric device using the same - Google Patents
Secondary battery, battery module, battery pack, and electric device using the same Download PDFInfo
- Publication number
- CN115842112A CN115842112A CN202210007504.0A CN202210007504A CN115842112A CN 115842112 A CN115842112 A CN 115842112A CN 202210007504 A CN202210007504 A CN 202210007504A CN 115842112 A CN115842112 A CN 115842112A
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- Prior art keywords
- secondary battery
- fluorine
- electrolyte
- antimony
- battery
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- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 72
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- 239000000654 additive Substances 0.000 claims abstract description 67
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- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims abstract description 31
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 25
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- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- ZUSRFDBQZSPBDV-UHFFFAOYSA-N n-[bis(dimethylamino)stibanyl]-n-methylmethanamine Chemical compound CN(C)[Sb](N(C)C)N(C)C ZUSRFDBQZSPBDV-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- YGBFTDQFAKDXBZ-UHFFFAOYSA-N tributyl stiborite Chemical compound [Sb+3].CCCC[O-].CCCC[O-].CCCC[O-] YGBFTDQFAKDXBZ-UHFFFAOYSA-N 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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Abstract
The application provides a secondary battery, a battery module, a battery pack and an electric device thereof. The secondary battery comprises a negative pole piece and electrolyte, wherein the negative pole piece contains a negative active material, and the negative active material comprises a kernel and a coating layer which is arranged on the surface of the kernel and contains an antimony element; the electrolyte contains lithium salt and a fluorine-containing additive, wherein the fluorine-containing additive is a fluorine-containing ester monocyclic compound; wherein the molar ratio of the antimony element to the fluorine-containing additive is 1 to 10, optionally 0.9 to 10. In this application, through using above-mentioned secondary battery, help forming the SEI film that LiF content is high at the negative pole piece, can effectively prevent the coinsertion of solvent molecule, avoid solvent molecule coinsertion and to negative electrode material's destruction, when having reduced the decomposition of solvent in the electrolyte, can improve cycle performance, prolong secondary battery's life-span.
Description
Technical Field
The present application relates to the field of battery technology, and in particular, to a secondary battery, a battery module, a battery pack, and an electric device using the same.
Background
In recent years, with the increasing demand for clean energy, secondary batteries have been widely used in energy storage power systems such as hydraulic power, thermal power, wind power, and solar power stations, and in various fields such as electric tools, military equipment, and aerospace. As the application field of the secondary battery is greatly expanded, higher requirements are also put on the performance thereof.
In order to further improve the endurance and service life of the secondary battery, and improve the user experience, how to improve the cycle performance and the service life of the secondary battery has become a technical problem to be solved urgently.
Disclosure of Invention
Technical problem to be solved by the present application
The present invention has been made in view of the above problems, and an object thereof is to provide a secondary battery, a battery module, a battery pack, and an electric device using the same, each of which has a long cruising power and a long service life.
Means for solving the problems
In order to achieve the above object, the present application provides a secondary battery, a battery module, a battery pack, and an electric device thereof.
Secondary battery
A first aspect of the present application provides a secondary battery including a negative electrode sheet and an electrolyte; the negative pole piece contains a negative active material, and the negative active material comprises a kernel and a coating layer which is arranged on the surface of the kernel and contains an antimony element; the electrolyte contains lithium salt and a fluorine-containing additive, wherein the fluorine-containing additive is a fluorine-containing ester monocyclic compound; wherein the molar ratio of the antimony element to the fluorine-containing additive is 1: 20-10: 1, optionally 0.9: 10-6: 10.
In the application, the coating layer containing the antimony element is arranged on the surface of the inner core and is used as a negative active material, and the negative pole piece containing the negative active material is applied to the electrolyte containing lithium salt and the fluorine-containing additive. During the charging process of the secondary battery, lithium salt in the electrolyte can ionize free lithium ions, and the free lithium ions can react with antimony in the negative pole piece to form lithium-containing lithium 3 A film layer of Sb. When solvent molecules and fluorine-containing esters in the electrolyteWhen the monocyclic compound diffuses to the surface of the negative pole piece, the fluorine-containing ester monocyclic compound and Li on the surface of the negative pole piece are opposite to other solvent molecules in the electrolyte 3 Sb has stronger binding energy and is preferentially adsorbed to Li 3 The surface of the Sb film layer and promotes the decomposition of the fluorine-containing additive to generate a stable solid electrolyte interface film (SEI film) of which the main component is LiF. LiF is an inorganic compound, and has better stability compared with organic components in other SEI films. When the content of LiF in the SEI film is high, the film strength can be improved, cracking of the SEI film caused by expansion is resisted, co-embedding of solvent molecules is effectively prevented, damage to an electrode material due to co-embedding of the solvent molecules is avoided, and meanwhile decomposition of an electrolyte solvent is reduced. Therefore, the cycle performance of the secondary battery is improved, and the service life of the secondary battery is prolonged.
In the application, a fluorine-containing ester monocyclic compound is selected as the fluorine-containing additive. Compared with the fluorine-containing ester compound with more rings, the fluorine-containing ester monocyclic compound has lower steric hindrance and Li 3 The binding energy of Sb is stronger, so that Sb is favorably adsorbed on the surface of the negative pole piece in preference to solvent molecules and decomposed to form an SEI film with higher stability.
The molar ratio of the antimony element to the fluorine-containing additive in the secondary battery is defined, so that Li is formed under the condition of not influencing other components of a battery system 3 The good adsorption relationship between Sb and the fluorine-containing additive prevents the problems of excessive consumption of solvent, excessive loss of active ions, uneven coating of an SEI film and the like.
In any embodiment, the coating layer containing antimony element contains at least one of antimony simple substance, antimony oxide and antimony trifluoride, and optionally antimony simple substance. In the present application, at least one of antimony simple substance, antimony oxide and antimony trifluoride is used as a coating layer of a negative electrode active material, and the coating layer can react with lithium ions in an electrolyte to form a coating layer containing Li 3 Sb film layer, and further adsorbing fluorine-containing additives to promote the decomposition of the fluorine-containing additives to form an SEI film with high LiF content. With Sb 2 O 3 For example, the reaction formula of the lithium ion-containing electrolyte with lithium ions is as follows:
Sb 2 O 3 +6Li + →2Sb 3+ +3Li 2 O、
3Li + +Sb→Li 3 Sb、
SbF 3 +3Li + →3LiF+Sb 3+ 。
therefore, the co-intercalation of solvent molecules can be effectively prevented, the damage to the electrode material caused by the co-intercalation of the solvent molecules is avoided, the cycle performance of the secondary battery is improved, and the service life of the secondary battery is prolonged.
In any embodiment, the coating has a thickness of 5nm to 1000nm, optionally 20nm to 400nm. The present application can improve the cycle performance of the secondary battery without affecting the capacity and extend the service life of the secondary battery by controlling the thickness of the coating layer within a suitable range.
In any embodiment, the coating layer is present in an amount of 0.5% to 20%, optionally 1% to 10%, by mass based on the total mass of the anode active material. Therefore, the mass percentage of the coating layer is controlled within a proper range, so that on one hand, a uniform SEI film with a stable structure can be formed on the surface of the negative pole piece, and the protection effect on the negative pole material is good; meanwhile, the consumption of active lithium can be ensured to be low, and the battery capacity is ensured, so that the cycle performance improvement effect of the secondary battery is ensured, and the service life of the secondary battery is prolonged.
In any embodiment, the fluorine-containing additive comprises at least one of fluoroethylene carbonate, phenyl trifluoroacetate, allyltris (2,2,2-trifluoroethyl) carbonate, optionally fluoroethylene carbonate or phenyl trifluoroacetate. When the fluorine-containing additive is selected, the fluorine-containing additive is mixed with Li relative to other solvent molecules 3 Sb has a stronger binding energy and a stronger attraction force with each other, and therefore Sb can be preferentially adsorbed to Li 3 And decomposing the Sb film layer to generate an SEI film with high LiF content and stability. LiF is an inorganic compound, and has better stability compared with organic components in other SEI films. When the content of LiF in the SEI film is higher, the strength and the resistance of the film can be improvedThe swelling leads to the cracking of the SEI film, thereby effectively preventing the co-intercalation of solvent molecules and avoiding the damage to the electrode material caused by the co-intercalation of the solvent molecules. Therefore, the fluorine-containing additive in the range is selected, the stable SEI film with high LiF content can be generated, the co-embedding of solvent molecules can be effectively prevented, the damage to an electrode material due to the co-embedding of the solvent molecules is avoided, and the cycle performance and the service life of the secondary battery are further improved.
In any embodiment, the fluorine-containing additive is present in an amount of 0.5% to 20%, alternatively 2% to 10%, by mass based on the total mass of the electrolyte. By controlling the mass percent of the fluorine-containing additive in a proper range, on one hand, the low consumption of the solvent caused by the formation of the SEI film can be ensured, the decomposition of the solvent can be prevented, the battery capacity can be ensured, and the use of the full life cycle can be met; meanwhile, the solvent in the electrolyte can be ensured to be in a proper proportion, and the conditions of an electrolyte system, solubility, viscosity and the like are ensured to be in a good state, so that the cycle performance of the secondary battery is improved, and the service life of the secondary battery is prolonged.
In any embodiment, the molar concentration of the lithium salt in the electrolyte is 0.7M to 1.5M.
In any embodiment, the core comprises at least one of graphite, hard carbon, soft carbon, lithium titanate, tin-based materials, nickel-based materials, and alloy materials.
A second aspect of the present application provides a battery module including the secondary battery of the first aspect of the present application. The battery module has good cycle performance and long service life.
A third aspect of the present application provides a battery pack including the battery module of the second aspect of the present application. The battery pack has good cycle performance and a long service life.
A fourth aspect of the present application provides an electric device including at least one selected from the secondary battery of the first aspect of the present application, the battery module of the second aspect of the present application, or the battery pack of the third aspect of the present application. The electric device has good cycle performance and long service life.
Advantageous effects
The application provides a secondary battery, which comprises a negative pole piece and electrolyte, wherein the negative pole piece contains a negative active material, and the surface of the core of the negative active material is provided with a coating layer containing an antimony element; the electrolyte contains lithium salt and a fluorine-containing additive, wherein the fluorine-containing additive is a fluorine-containing ester monocyclic compound; wherein the molar ratio of the antimony element to the fluorine-containing additive is 1: 20-10: 1, optionally 0.9: 10-6: 10. In the present application, by using the secondary battery, li-containing material can be formed on the surface of the negative electrode sheet after charging 3 The Sb film layer is decomposed by preferentially adsorbing the fluorine-containing additive in the electrolyte to form an SEI film with high LiF content, so that the co-intercalation of solvent molecules can be effectively prevented, the damage to a negative electrode material caused by the co-intercalation of the solvent molecules is avoided, the decomposition of the solvent in the electrolyte is reduced, the cycle performance can be improved, and the service life of a secondary battery is prolonged.
Drawings
Fig. 1 is a schematic view of an anode active material according to an embodiment of the present application.
Fig. 2 is a result of cycle performance test of secondary batteries made of the negative electrode active materials obtained in example 1 of the present application and comparative example 1.
Fig. 3 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 4 is an exploded view of the secondary battery according to the embodiment of the present application shown in fig. 3.
Fig. 5 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 6 is a schematic diagram of a battery pack according to an embodiment of the present application.
Fig. 7 is an exploded view of the battery pack according to the embodiment of the present application shown in fig. 6.
Fig. 8 is a schematic diagram of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Description of the reference numerals:
1, a battery pack; 2, putting the box body on the box body; 3, discharging the box body; 4 a battery module; 5 a secondary battery; 51 a housing; 52 an electrode assembly; 53 a cap assembly.
Detailed Description
Hereinafter, embodiments specifically disclosing the secondary battery, the battery module, the battery pack, and the electric device according to the present application will be described in detail with reference to the drawings as appropriate. But detailed description thereof will be omitted unnecessarily. For example, detailed descriptions of already known matters and repetitive descriptions of actually the same configurations may be omitted. This is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. The drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited in the claims.
As disclosed herein, a "range" is defined in terms of lower and upper limits, with a given range being defined by the selection of one lower limit and one upper limit, which define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Further, if the minimum range values of 1 and 2 are listed, and if the maximum range values of 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not otherwise specified.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
The inventor finds that the secondary battery, especially at the position of a negative pole piece of the secondary battery, has the problems of solvent molecule co-intercalation and excessive solvent decomposition, and is an important influence factor for restricting the cycle performance and the service life of the secondary battery. The inventor of the application can effectively improve the cycle performance of the secondary battery and prolong the service life of the secondary battery by arranging the coating layer containing the antimony substance on the surface of the core of the negative active material and adding the special additive into the electrolyte.
In view of this, a first embodiment of the present application provides a secondary battery including a negative electrode sheet and an electrolyte; the negative pole piece contains a negative active material, and the negative active material comprises a kernel and a coating layer which is arranged on the surface of the kernel and contains an antimony element; the electrolyte contains lithium salt and a fluorine-containing additive, wherein the fluorine-containing additive is a fluorine-containing ester monocyclic compound; wherein the molar ratio of the antimony element to the fluorine-containing additive is 1 to 10, optionally 0.9 to 10.
As shown in fig. 1, in the present application, a coating layer containing an antimony element is provided on the surface of a core, and the coating layer is used as a negative electrode active material, and a negative electrode sheet containing the negative electrode active material is applied to an electrolyte containing a lithium salt and a fluorine-containing additive. During the charging process of the secondary battery, lithium salt in the electrolyte can ionize free lithium ions, and the free lithium ions can react with antimony in the negative pole piece to form lithium-containing lithium 3 A film layer of Sb. When solvent molecules in the electrolyte and the fluorine-containing ester monocyclic compound are diffused to the surface of the negative pole piece at the same time, the fluorine-containing ester monocyclic compound and Li on the surface of the negative pole piece are opposite to other solvent molecules in the electrolyte 3 Sb has stronger binding energy and stronger mutual attraction, and can be preferentially adsorbed to Li 3 The surface of the Sb film layer and promotes the decomposition of the fluorine-containing additive to generate a stable solid electrolyte interface film (SEI film) of which the main component is LiF. In the SEI film of the application, liF is an inorganic compound, and compared with organic components in other SEI films, the stability is better. When the content of LiF in the SEI film is high, the strength of the film can be improved, cracking of the SEI film due to swelling can be resisted, co-intercalation of solvent molecules can be effectively prevented, damage to electrode materials due to co-intercalation of the solvent molecules can be avoided, decomposition of an electrolyte solvent can be reduced, the cycle performance of the secondary battery can be improved, and the service life of the secondary battery can be prolonged, as shown in fig. 2.
In the application, the fluorine-containing ester monocyclic compound is used as the fluorine-containing additive, and compared with the fluorine-containing ester compound with more rings, the fluorine-containing ester monocyclic compound has lower steric hindrance and is Li 3 The binding energy of Sb is stronger. The binding energy is the free energy of the binding reaction of two substances, and the smaller the binding energy value is, the easier the two substances are bound.
The secondary battery provided by the application can meet the molar ratio of the antimony element to the fluorine-containing additive in an initial state, particularly within 10 cycle turns of charge and discharge. After 1000 cycles of charge and discharge, the molar ratio of the two can be kept in the range of 1:5-40, optionally 1. By limiting the molar ratio of the antimony element to the fluorine-containing additive in the secondary battery, the formation of Li can be ensured under the condition of not influencing other components of a battery system 3 The good adsorption relationship between Sb and the fluorine-containing additive prevents the problems of excessive consumption of solvent, excessive loss of active ions, uneven coating of an SEI film and the like.
In addition, in the present application, the coating layer on the surface of the negative electrode active material is preferably generated in situ, and the coating layer occupies a small volume in the negative electrode active material, so that the secondary battery provided by the present application is suitable for the case where the space is limited and the requirements for weight and energy density are high, but not limited thereto.
In the present application, the content of antimony and the content of fluorine-containing additive can be measured by methods known in the art. For example, the content of antimony can be measured by an inductively coupled plasma spectrometer (ICP), for example, ICP-3000 from the company sky; the amount of fluorochemical additive can be determined by GC testing, for example, using an instrument such as GC-2014C from Shimadzu. The ratio of the two can be obtained by calculation.
In some embodiments, the coating layer containing antimony element contains at least one of antimony element, antimony oxide and antimony trifluoride, and optionally antimony element.
In the present application, at least one of antimony simple substance, antimony oxide and antimony trifluoride is used as a coating layer of a negative electrode active material, and the coating layer can react with lithium ions in an electrolyte to form a coating layer containing Li 3 And the Sb film further adsorbs the fluorine-containing additive, so that the Sb film is decomposed to form an SEI film with high LiF content. With Sb 2 O 3 For example, it is reacted with lithium in an electrolyteThe reaction formula for ion generation is:
Sb 2 O 3 +6Li + →2Sb 3+ +3Li 2 O、
3Li + +Sb→Li 3 Sb、
SbF 3 +3Li + →3LiF+Sb 3+ 。
therefore, the co-intercalation of solvent molecules can be effectively prevented, the damage to the electrode material caused by the co-intercalation of the solvent molecules is avoided, the cycle performance of the secondary battery is improved, and the service life of the secondary battery is prolonged.
In some embodiments, the coating has a thickness of 5nm to 1000nm, optionally 20nm to 400nm. The present application can improve the cycle performance of the secondary battery without affecting the capacity and extend the service life of the secondary battery by controlling the thickness of the coating layer within a suitable range.
In the present application, the thickness of the cladding layer can be tested using methods known in the art. As an example, the characterization test can be performed using a Transmission Electron Microscope (TEM), such as the JEM-2100F instrument from JEOL.
In some embodiments, the coating layer is present in an amount of 0.5% to 20%, optionally 1% to 10%, by mass based on the total mass of the anode active material.
Therefore, the mass percentage of the coating layer is controlled within a proper range, so that on one hand, a uniform SEI film with a stable structure can be formed on the surface of the negative pole piece, and the protection effect on the negative pole material is good; meanwhile, the consumption of active lithium can be ensured to be low, and the battery capacity is ensured, so that the cycle performance of the secondary battery is improved, and the service life of the secondary battery is prolonged.
In some embodiments, the fluorine-containing additive comprises at least one of fluoroethylene carbonate, phenyl trifluoroacetate, allyltris (2,2,2-trifluoroethyl) carbonate, optionally fluoroethylene carbonate or phenyl trifluoroacetate.
When the fluorine-containing additive is selected, the additive is relativelyOther solvent molecules, the above with Li 3 Sb has a stronger binding energy and a stronger attraction to each other, and therefore can be preferentially adsorbed to Li 3 And decomposing the Sb film layer to generate an SEI film with high LiF content and stability. LiF is an inorganic compound, and has better stability compared with organic components in other SEI films. When the LiF content in the SEI film is high, the film strength can be improved, cracking of the SEI film caused by expansion is resisted, co-intercalation of solvent molecules is effectively prevented, and damage to an electrode material due to co-intercalation of the solvent molecules is avoided. Therefore, the fluorine-containing additive within the range can generate the SEI film with high and stable LiF content, can effectively prevent the co-embedding of solvent molecules, avoids the damage to electrode materials caused by the co-embedding of the solvent molecules, and further improves the cycle performance and the service life of the secondary battery.
In some embodiments, the fluorine-containing additive is present in an amount of 0.5% to 20%, optionally 2% to 10%, by mass based on the total mass of the electrolyte. The secondary battery provided by the application has the advantages that the fluorine-containing additive can meet the mass percentage range in the initial state, particularly within 10 cycle turns of charge and discharge.
Therefore, the mass percent of the fluorine-containing additive is controlled within a proper range, so that on one hand, the low consumption of the solvent caused by the formation of the SEI film can be ensured, the decomposition of the solvent can be prevented, the battery capacity can be ensured, and the use in the whole life cycle can be met; meanwhile, the solvent in the electrolyte can be ensured to be in a proper proportion, and the conditions of an electrolyte system, solubility, viscosity and the like are ensured to be in a good state, so that the cycle performance of the secondary battery is improved, and the service life of the secondary battery is prolonged.
In some embodiments, the molar concentration of the lithium salt in the electrolyte is 0.7M to 1.5M.
In some embodiments, the inner core may employ a negative active material for a battery, which is well known in the art. As an example, the inner core may comprise at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, tin-based materials, nickel-based materials, lithium titanate, alloy materials, and the like. The alloy material may be selected from silicon-based materials, which may be selected from at least one of elemental silicon, silicon oxy-compounds, silicon carbon compounds, silicon nitrogen compounds, and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin-oxygen compounds, and tin alloys. The present application is not limited to these materials, however, and other conventional materials that can be used as a battery negative active material may be used as the core. These materials may be used alone or in combination of two or more as the core.
In some embodiments, the negative electrode tab further comprises a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, the negative electrode film layer comprising the negative electrode active material. As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode film layer is disposed on either or both of the two surfaces opposite to the negative electrode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (e.g., a substrate of PP, PET, PBT, PS, PE, etc.).
In some embodiments, the anode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode film layer may also optionally include other adjuvants, such as thickeners (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet can be prepared by the following method:
providing a precursor containing antimony and a kernel, mixing the precursor containing antimony and the kernel, and calcining to obtain a negative active material, wherein the negative active material comprises the kernel and a coating layer containing antimony arranged on the surface of the kernel; dispersing the components for preparing the negative electrode plate, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (such as deionized water) to form negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and drying, cold pressing and the like to obtain the negative electrode pole piece.
In the application, the preparation method of the negative pole piece can be used for simply and easily preparing the negative pole piece, and has the advantages of low energy consumption and low cost; in addition, by the method, the precursor containing the antimony element can be uniformly coated on the surface of the inner core, so that the negative pole piece meeting the conditions of the application can be obtained.
In some embodiments, the elemental antimony-containing precursor comprises an antimony salt comprising at least one of antimony trichloride, antimony nitrate, antimony sulfate, antimony acetate, poly (antimony ethylene glycol), tris (dimethylamino) antimony, triphenylantimony, antimony butoxide, triphenylantimony dichloride, antimony (III) ethoxide, triphenylantimony dibromide, fluoroantimonic acid hexahydrate; the coating layer containing the antimony element comprises at least one of an antimony simple substance, an antimony oxide and antimony trifluoride; the core contains at least one of graphite, hard carbon, soft carbon, lithium titanate, tin-based materials, nickel-based materials and alloy materials.
In some embodiments, the mixing step comprises:
and mixing the precursor containing the antimony element and the inner core in an aqueous solution, adding hydrochloric acid to keep the pH value of the solution at 2-4, stirring until the solution is uniformly mixed, and evaporating the solvent.
In the present application, hydrolysis of the precursor containing antimony can be effectively suppressed by controlling the pH range in the mixing step. When the pH value is higher than 4, the precursor containing the antimony element is easy to hydrolyze, and the precursor containing the antimony element cannot be uniformly coated on the surface of the inner core; when the pH value is less than 2, the reaction conditions are too acidic, and the reaction vessel is corroded. This enables the formation of a uniform coating layer containing an antimony element on the surface of the core.
In some embodiments, the calcining step comprises:
the sintering temperature is controlled to be 400-800 ℃, the sintering time is 4-12 h, and the sintering is carried out in the inert gas atmosphere.
In the calcining step, when the sintering temperature is low and the sintering time is short, the problems of overlong reduction time and poor reduction effect can be caused; the sintering temperature is high, and the sintering time is long, so that the curing phenomenon can be caused, the coating layers of adjacent particles are fused together, and the problems of particle agglomeration and the like are caused; meanwhile, calcination needs to be performed in an inert gas atmosphere to protect the inner core from being consumed by oxidation. In this way, the sintering temperature, sintering time, and gas atmosphere are limited in the calcination step, and the negative electrode active material satisfying the conditions of the present application can be obtained.
The other parts of the secondary battery, the battery module, the battery pack, and the electric device according to the present invention will be described below with reference to the drawings as appropriate.
In one embodiment of the present application, a secondary battery is provided.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. In the process of charging and discharging the battery, active ions are embedded and separated back and forth between the positive pole piece and the negative pole piece. The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The isolating membrane is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the short circuit of the positive pole and the negative pole, and can enable ions to pass through. Each constituent element of the secondary battery will be described in detail below.
[ Positive electrode sheet ]
The positive pole piece includes the anodal mass flow body and sets up the anodal rete on anodal mass flow body at least one surface, anodal rete includes the anodal active material of the first aspect of this application.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode film layer is disposed on either or both of the two surfaces opposite to the positive electrode current collector.
In some embodiments, the positive electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material base material (e.g., a base material of polypropylene (PP), PET, PBT, polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive active material may employ a positive active material for a battery, which is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: olivine structured lithium-containing phosphates, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a positive electrode active material of a battery may be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, examples of the lithium transition metal oxide may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g., liNiO) 2 ) Lithium manganese oxides (e.g., liMnO) 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g., liNi) 1/3 Co 1/3 Mn 1/3 O 2 (may also be abbreviated as NCM) 333 )、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (may also be abbreviated as NCM) 523 )、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (may also be abbreviated as NCM) 211 )、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (may also be abbreviated as NCM) 622 )、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (may also be abbreviated as NCM) 811 ) Lithium nickel cobalt aluminum oxides (e.g., liNi) 0.85 Co 0.15 Al 0.05 O 2 ) And modified compounds thereof, and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO) 4 (may also be abbreviated as LFP)), a composite material of lithium iron phosphate and carbon, and lithium manganese phosphate (e.g., liMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and the like to obtain the positive electrode piece.
[ negative electrode sheet ]
The negative electrode plate is described in detail above.
[ electrolyte ]
The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The kind of the electrolyte is not particularly limited and may be selected as desired. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolytic solution. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium dioxaoxalato borate, lithium difluorodioxaoxalato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte includes an additive. For example, the additives may include a negative electrode film-forming additive, a positive electrode film-forming additive, and may further include additives capable of improving certain properties of the battery, such as an additive for improving overcharge properties of the battery, an additive for improving high-temperature or low-temperature properties of the battery, and the like. In the present application, the electrolyte includes a fluorine-containing additive that is a fluorine-containing ester monocyclic compound.
[ isolation film ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known separator having a porous structure and good chemical and mechanical stability may be used.
In some embodiments, the material of the isolation film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an exterior package. The exterior package may be used to enclose the electrode assembly and electrolyte.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The outer package of the secondary battery may also be a pouch, such as a pouch-type pouch. The material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
The shape of the secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, or any other arbitrary shape. For example, fig. 3 is a secondary battery 5 of a square structure as an example.
In some embodiments, referring to fig. 4, the overwrap may include a housing 51 and a cover plate 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose to form an accommodating cavity. The housing 51 has an opening communicating with the accommodating chamber, and a cover plate 53 can be provided to cover the opening to close the accommodating chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. An electrode assembly 52 is enclosed within the receiving cavity. The electrolyte is impregnated into the electrode assembly 52. The number of electrode assemblies 52 contained in the secondary battery 5 may be one or more, and those skilled in the art can select them according to the actual needs.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
Fig. 5 is a battery module 4 as an example. Referring to fig. 5, in the battery module 4, a plurality of secondary batteries 5 may be arranged in series along the longitudinal direction of the battery module 4. Of course, the arrangement may be in any other way. The plurality of secondary batteries 5 may be further fixed by a fastener.
Alternatively, the battery module 4 may further include a case having an accommodation space in which the plurality of secondary batteries 5 are accommodated.
In some embodiments, the battery modules may be assembled into a battery pack, and the number of the battery modules contained in the battery pack may be one or more, and the specific number may be selected by one skilled in the art according to the application and the capacity of the battery pack.
Fig. 6 and 7 are a battery pack 1 as an example. Referring to fig. 6 and 7, a battery pack 1 may include a battery case and a plurality of battery modules 4 disposed in the battery case. The battery box comprises an upper box body 2 and a lower box body 3, wherein the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. A plurality of battery modules 4 may be arranged in any manner in the battery box.
In addition, this application still provides a power consumption device, power consumption device includes at least one in secondary battery, battery module or the battery package that this application provided. The secondary battery, the battery module, or the battery pack may be used as a power source of the electric device, and may also be used as an energy storage unit of the electric device. The powered device may include a mobile device (e.g., a mobile phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship, a satellite, an energy storage system, etc., but is not limited thereto.
As the electricity-using device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirement thereof.
Fig. 8 is an electric device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle or a plug-in hybrid electric vehicle and the like. In order to meet the demand of the electric device for high power and high energy density of the secondary battery, a battery pack or a battery module may be used.
As another example, the device may be a cell phone, a tablet, a laptop, etc. The device is generally required to be thin and light, and a secondary battery may be used as a power source.
Examples
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) Preparation of negative active material
95g of graphite and 5g of SbCl 3 After being uniformly mixed by a liquid phase method, the sample is placed in Ar/H 2 (5％H 2 ) In an atmosphere of (2), calcining for 6h at 500 ℃ to obtain the negative active material. The physical parameters of the negative electrode active material are shown in table 1 below.
(2) Preparation of negative pole piece
Dispersing the negative active material, the conductive agent carbon black, the binder Styrene Butadiene Rubber (SBR) and the sodium carboxymethyl cellulose (CMC) in deionized water, and fully stirring and uniformly mixing to form negative slurry; and coating the negative electrode slurry on a copper foil of a negative current collector, and drying and cold pressing to obtain a negative electrode pole piece.
(3) Preparation of secondary battery
Lithium manganese phosphate used as a positive electrode material, acetylene black used as a conductive agent and polyvinylidene fluoride (PVDF) used as a binder are fully stirred and uniformly mixed in an N-methylpyrrolidone solvent system according to the weight ratio of 94: 3, and then the mixture is coated on an aluminum foil to be dried and cold-pressed, so that a positive electrode piece is obtained.
A porous polymer film made of Polyethylene (PE) was used as a separator.
And overlapping the positive plate, the isolating film and the negative plate in sequence to enable the isolating film to be positioned between the positive and negative electrodes to play an isolating role, and winding to obtain the bare cell.
The electrolyte is fluoroethylene carbonate (FEC)/(ethylene carbonate (EC) + diethyl carbonate (DEC)) (mass ratio is 5: 95), and the volume ratio of EC to DEC is 1: 1.
And placing the bare cell in an outer package, injecting the electrolyte and packaging to obtain the secondary battery.
Examples 2 to 3
Secondary batteries of examples 2 to 3 were prepared in the same manner as in example 1, except that the coating layer thickness of the negative electrode active material was changed by adjusting the input amount of the antimony-containing precursor in the raw material as shown in table 1 below.
Example 4
A secondary battery of example 4 was prepared in the same manner as in example 1, except that the coating layer thickness of the negative electrode active material was changed by adjusting the input amount of the antimony-containing precursor in the raw material, and the addition amount of FEC was adjusted, as shown in table 1 below.
Example 5
A secondary battery of example 5 was prepared in the same manner as in example 1, except that FEC was changed to phenyl trifluoroacetate as shown in table 1 below.
Examples 6 to 7
Secondary batteries of examples 6 to 7 were produced in the same manner as in example 1, except that FEC was changed to phenyl trifluoroacetate as shown in the following table 1, and the addition amount was adjusted.
Example 8
A secondary battery of example 8 was prepared in the same manner as in example 1, except that the coating layer thickness of the negative electrode active material was changed by adjusting the input amount of the antimony-containing precursor in the raw material, and the addition amount of FEC was adjusted, as shown in table 1 below.
Example 9
(1) Preparation of negative active material
95g of graphite and 5g of Sb 2 O 3 And putting the mixture into a ball milling tank, and performing ball milling for 10 hours at the rotating speed of 400r/min to obtain the cathode active material.
(2) Preparation of negative pole piece
Dispersing the negative electrode active material, the conductive agent carbon black, the binder Styrene Butadiene Rubber (SBR) and the sodium carboxymethylcellulose (CMC) in deionized water, and fully stirring and uniformly mixing to form negative electrode slurry; and coating the negative electrode slurry on a copper foil of a negative current collector, and drying and cold pressing to obtain a negative electrode pole piece.
(3) Preparation of secondary battery
Lithium manganese phosphate used as a positive electrode material, acetylene black used as a conductive agent and polyvinylidene fluoride (PVDF) used as a binder are fully stirred and uniformly mixed in an N-methylpyrrolidone solvent system according to the weight ratio of 94: 3, and then the mixture is coated on an aluminum foil to be dried and cold-pressed, so that a positive electrode piece is obtained.
A porous polymer film made of Polyethylene (PE) was used as a separator.
And overlapping the positive plate, the isolating film and the negative plate in sequence to enable the isolating film to be positioned between the positive and negative electrodes to play an isolating role, and winding to obtain the bare cell.
The electrolyte is fluoroethylene carbonate (FEC)/(ethylene carbonate (EC) + diethyl carbonate (DEC)) (mass ratio is 5: 95), and the volume ratio of EC to DEC is 1: 1.
And placing the bare cell in an outer package, injecting the electrolyte and packaging to obtain the secondary battery.
Example 10
Except that Sb was added to the raw materials as shown in Table 1 below 2 O 3 Adjusted to SbF 3 Except that, a secondary battery of example 10 was prepared in the same manner as in example 9.
Comparative example 1
A secondary battery of comparative example 1 was prepared in the same manner as in example 1, except that the precursor containing antimony was not added during the preparation of the anode active material, as shown in table 1 below.
Comparative example 2
A secondary battery of comparative example 2 was prepared in the same manner as example 1, except that FEC was not added to the electrolyte as shown in table 1 below.
Comparative example 3
A secondary battery of comparative example 3 was prepared in the same manner as in example 1, except that the addition amount of FEC was adjusted as shown in table 1 below.
Comparative example 4
A secondary battery of comparative example 4 was prepared in the same manner as in example 1, except that FEC was changed to 2-fluoro-1-naphthol as shown in table 1 below.
Comparative example 5
A secondary battery of comparative example 5 was prepared in the same manner as in example 1, except that the coating layer thickness of the negative electrode active material was changed by adjusting the input amount of the antimony-containing precursor in the raw material and the addition amount of FEC was adjusted as shown in table 1 below.
Next, a method for testing the secondary battery will be explained.
(1) Initial capacity test
Charging the secondary battery prepared by the method to 4.2V at 0.33C in a constant temperature environment of 25 ℃, then charging the secondary battery to a current of less than or equal to 0.05C at a constant voltage under 4.2V, standing for 5min, then discharging the secondary battery to 2.8V at 0.33C, and testing to obtain the initial capacity of the secondary battery.
(2) Capacity Retention Rate test
And (3) charging the prepared secondary battery to 4.2V at 1C under a constant temperature environment of 60 ℃, then charging the secondary battery to a current of less than or equal to 0.05C at a constant voltage under 4.2V, standing for 5min, then discharging the secondary battery to 2.8V at 1C, circulating for 500 circles, and dividing the capacity obtained after 500 circles by the initial capacity to obtain the capacity retention rate.
Table 2: results of Performance test of examples 1 to 10 and comparative examples 1 to 5
As can be seen from examples 1 to 10 in table 2, the secondary battery of the present application has good cycle performance and service life when the type, thickness, and mass percentage of antimony element in the coating layer of the negative active material in the secondary battery, the type, mass percentage of the fluorine-containing additive in the electrolyte, and the molar ratio of the particles containing antimony element to the fluorine-containing additive are within the ranges of the present application.
As is clear from the comparison between example 1 and comparative examples 1-2 in Table 2, the coating layer containing antimony element and the fluorine-containing additive were found to be indispensable. When a conventional negative active material is directly selected and is not coated with antimony, an SEI film formed on the surface of a secondary battery contains a large amount of organic components after the secondary battery is charged, so that the stability of the SEI film is insufficient, the SEI film is damaged due to the expansion of an anode, and active lithium is continuously consumed for reconstruction, so that the cycle performance of the secondary battery is poor; when the electrolyte is not added with the fluorine-containing additive, after the secondary battery is charged, the SEI film generated on the surface of the negative electrode material can absorb solvent molecules in the electrolyte, so that the capacity is quickly attenuated. Compared with the existing secondary battery, the secondary battery has better cycle performance.
As is clear from comparison between example 1 and comparative example 4 in Table 2, when an ester polycyclic compound is used as an additive, although it contains fluorine, steric hindrance increases due to polycyclic molecules, and Li is produced 3 The Sb film layer is difficult to adsorb and bind, and does not have adsorption priority compared to the remaining components in the electrolyte, and therefore, it also absorbs solvent molecules in the electrolyte, resulting in rapid capacity fading, failing to improve cycle performance of the secondary battery.
As is clear from the comparison between example 5 and comparative example 3 in the above Table 2, and between example 2 and comparative example 5, when the molar ratio of antimony element to fluorine-containing additive exceeds the range of the present application, li 3 Sb and the fluorine-containing additive can not form a good adsorption relation, so that the problem of excessive loss of active ions is caused, and the initial capacity of the secondary battery is reducedAnd the cycle performance of the secondary battery cannot be improved.
As is apparent from examples 5 to 7 and comparative example 3 in table 2 above, when the amount of the fluorine-containing additive added to the secondary battery is within an appropriate range, the improvement effect on the cycle performance can be secured; when the additive containing the fluorine additive in the secondary battery is too much, conditions such as an electrolyte system, solubility, viscosity and the like cannot be ensured to be in a good state. Therefore, it is necessary to control the amount of the fluorine-containing additive to be in an appropriate range.
As can be seen from examples 1 to 3 in table 2 above, when the content of antimony element in the secondary battery is within a suitable range, a good improvement effect on the cycle performance can be ensured; when the content of antimony in the secondary battery is too much or too little, the cycle performance of the secondary battery is affected to some extent. In order to ensure that a uniform and stable SEI film can be formed on the surface of the negative pole piece and the consumption of active lithium is low, the content of antimony element needs to be controlled within a proper range so as to ensure a good improvement effect on the cycle performance of the secondary battery.
The present application is not limited to the above embodiments. The above embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exhibiting the same operation and effect within the technical scope of the present application are all included in the technical scope of the present application. In addition, various modifications that can be conceived by those skilled in the art are applied to the embodiments and other embodiments are also included in the scope of the present application, in which some of the constituent elements in the embodiments are combined and constructed, without departing from the scope of the present application.
Claims (11)
1. A secondary battery, characterized by comprising: a negative pole piece and an electrolyte,
the negative pole piece contains a negative active material, and the negative active material comprises an inner core and a coating layer which is arranged on the surface of the inner core and contains an antimony element;
the electrolyte contains lithium salt and a fluorine-containing additive, wherein the fluorine-containing additive is a fluorine-containing ester monocyclic compound;
wherein the molar ratio of the antimony element to the fluorine-containing additive is 1-10.
2. The secondary battery according to claim 1, wherein the coating layer containing antimony contains at least one of elemental antimony, antimony oxide, and antimony trifluoride, optionally elemental antimony.
3. The secondary battery according to any of claims 1 or 2, wherein the coating layer has a thickness of 5nm to 1000nm, optionally 20nm to 400nm.
4. The secondary battery of any of claims 1-3, wherein the coating layer is present in a mass percentage of 0.5% to 20%, optionally 1% to 10%, based on the total mass of the negative electrode active material.
5. The secondary battery of any of claims 1-4, wherein the fluorine-containing additive comprises at least one of fluoroethylene carbonate, phenyl trifluoroacetate, allyltris (2,2,2-trifluoroethyl) carbonate, optionally fluoroethylene carbonate or phenyl trifluoroacetate.
6. The secondary battery of any of claims 1-5, wherein the fluorine-containing additive is present in an amount of 0.5% to 20%, optionally 2% to 10%, by mass based on the total mass of the electrolyte.
7. The secondary battery according to any one of claims 1 to 6, wherein the molar concentration of the lithium salt in the electrolyte is 0.7M to 1.5M.
8. The secondary battery of any of claims 1-7, wherein the core comprises at least one of graphite, hard carbon, soft carbon, lithium titanate, tin-based materials, nickel-based materials, and alloy materials.
9. A battery module comprising the secondary battery according to any one of claims 1 to 8.
10. A battery pack comprising the battery module according to claim 9.
11. An electric device comprising at least one selected from the group consisting of the secondary battery according to any one of claims 1 to 8, the battery module according to claim 9, and the battery pack according to claim 10.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210007504.0A CN115842112A (en) | 2022-01-05 | 2022-01-05 | Secondary battery, battery module, battery pack, and electric device using the same |
| PCT/CN2022/137543 WO2023130887A1 (en) | 2022-01-05 | 2022-12-08 | Secondary battery, battery module, battery pack and electric device thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210007504.0A CN115842112A (en) | 2022-01-05 | 2022-01-05 | Secondary battery, battery module, battery pack, and electric device using the same |
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| CN115842112A true CN115842112A (en) | 2023-03-24 |
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| CN202210007504.0A Pending CN115842112A (en) | 2022-01-05 | 2022-01-05 | Secondary battery, battery module, battery pack, and electric device using the same |
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| CN (1) | CN115842112A (en) |
| WO (1) | WO2023130887A1 (en) |
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| US20130164604A1 (en) * | 2010-09-02 | 2013-06-27 | Nec Corporation | Secondary battery |
| CN103840223A (en) * | 2014-03-05 | 2014-06-04 | 芜湖凯尔电气科技有限公司 | Lithium battery filling agent |
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| CN109473718A (en) * | 2018-10-08 | 2019-03-15 | 河南师范大学 | A kind of high voltage withstanding electrolysis additive of lithium ion battery and non-aqueous electrolyte for lithium ion cell and application containing the additive |
| CN111313086A (en) * | 2019-12-24 | 2020-06-19 | 安徽圣格能源科技有限公司 | Electrolyte and lithium ion battery |
| CN112563463A (en) * | 2019-09-26 | 2021-03-26 | 宁德时代新能源科技股份有限公司 | Negative electrode additive, secondary battery, battery module, battery pack and device |
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| KR101601919B1 (en) * | 2013-12-12 | 2016-03-09 | 울산과학기술원 | Negative electrode active material, methode for manufacturing the same, and lithium rechargable battery including the same |
| JPWO2016072090A1 (en) * | 2014-11-06 | 2017-06-22 | 株式会社豊田自動織機 | Current collector for lithium ion secondary battery, method for producing the same, and nonaqueous electrolyte secondary battery |
| CN107623121B (en) * | 2017-10-18 | 2019-12-27 | 山东大学 | Metal-coated porous silicon composite electrode material and preparation method thereof |
| CN110957487A (en) * | 2019-12-18 | 2020-04-03 | 武汉大学 | Rechargeable battery system with high cycle stability |
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2022
- 2022-01-05 CN CN202210007504.0A patent/CN115842112A/en active Pending
- 2022-12-08 WO PCT/CN2022/137543 patent/WO2023130887A1/en unknown
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| US20130164604A1 (en) * | 2010-09-02 | 2013-06-27 | Nec Corporation | Secondary battery |
| CN103840223A (en) * | 2014-03-05 | 2014-06-04 | 芜湖凯尔电气科技有限公司 | Lithium battery filling agent |
| CN108400332A (en) * | 2018-03-09 | 2018-08-14 | 中国科学院青岛生物能源与过程研究所 | A kind of organic double ion embedded type flow battery |
| CN109473718A (en) * | 2018-10-08 | 2019-03-15 | 河南师范大学 | A kind of high voltage withstanding electrolysis additive of lithium ion battery and non-aqueous electrolyte for lithium ion cell and application containing the additive |
| CN112563463A (en) * | 2019-09-26 | 2021-03-26 | 宁德时代新能源科技股份有限公司 | Negative electrode additive, secondary battery, battery module, battery pack and device |
| CN111313086A (en) * | 2019-12-24 | 2020-06-19 | 安徽圣格能源科技有限公司 | Electrolyte and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023130887A1 (en) | 2023-07-13 |
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