WO2023137624A1 - 二次电池、电池模块、电池包以及用电装置 - Google Patents
二次电池、电池模块、电池包以及用电装置 Download PDFInfo
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- WO2023137624A1 WO2023137624A1 PCT/CN2022/072744 CN2022072744W WO2023137624A1 WO 2023137624 A1 WO2023137624 A1 WO 2023137624A1 CN 2022072744 W CN2022072744 W CN 2022072744W WO 2023137624 A1 WO2023137624 A1 WO 2023137624A1
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- Prior art keywords
- lithium
- secondary battery
- agent
- additive
- separator
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BVWQQMASDVGFGI-UHFFFAOYSA-N ethene propyl hydrogen carbonate Chemical compound C(CC)OC(O)=O.C=C BVWQQMASDVGFGI-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 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
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide 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
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 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
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 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
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000009783 overcharge test 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
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 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
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-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
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- 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
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- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
-
- 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
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Definitions
- the present application relates to the technical field of secondary batteries, in particular to a secondary battery, a battery module, a battery pack and an electrical device.
- secondary batteries have been widely used in energy storage power systems such as hydraulic, thermal, wind and solar power plants, as well as electric tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields. Due to the great development of secondary batteries, higher requirements have been put forward for their energy density, cycle performance and safety performance.
- a secondary battery is generally composed of a positive electrode, a negative electrode, a separator, and an electrolyte.
- charge transfer is usually achieved through the deintercalation of lithium ions in the positive and negative electrodes and the transfer of electrolytes in the electrolyte, thereby performing mutual conversion of chemical energy and electrical energy.
- the diaphragm is arranged between the positive pole piece and the negative pole piece, which mainly plays the role of preventing the short circuit of the positive and negative poles, and at the same time allows ions to pass through. Because of its position, the diaphragm plays a very important role in both realizing the working purpose of the secondary battery and ensuring the working safety of the secondary battery. Therefore, the performance of energy density, cycle performance and safety performance of the secondary battery can be further improved by studying and improving the design of the separator.
- the present application includes specific additives in the diaphragm of the secondary battery using a specific lithium supplement, thereby not only reducing the thermal shrinkage of the diaphragm, improving the overcharge prevention performance of the secondary battery, but also improving the utilization efficiency of the specific lithium supplement, so as to achieve the above purpose.
- the first aspect of the present application provides a secondary battery, which includes a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte, the secondary battery contains a lithium replenishing agent, and the lithium replenishing agent is at least one selected from the substances represented by the following general formula (I),
- the purity of the lithium supplement agent is greater than or equal to 90%; optionally greater than or equal to 95%.
- SEI solid electrolyte layer
- 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.
- FIG. 5 is a schematic diagram of a secondary battery according to an embodiment of the present application.
- FIG. 6 is an exploded view of the secondary battery according to one embodiment of the present application shown in FIG. 5 .
- Fig. 8 is a schematic diagram of a battery pack according to an embodiment of the present application.
- the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
- the mentioned method may also include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
- the term "or” is inclusive unless otherwise stated.
- the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by any of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
- the molecular weight of the nitrone derivatives with the structure represented by the formula (II) or the piperidine derivatives with the structure represented by the above formula (III) in the molecule is large, after neutralizing these free electrons or negative ions, other free harmful small molecules will not be produced, but will be stably fixed on the separator, so the cycle performance of the secondary battery will not be damaged.
- the nitrone derivatives having the structure represented by the formula (II) in the molecule or the piperidine derivatives having the structure represented by the above formula (III) in the molecule can play a bonding role with respect to the diaphragm substrate.
- the flexibility of the diaphragm is increased and the thermal shrinkage rate of the diaphragm is reduced, so that it is difficult for the metal particles introduced during processing to penetrate the diaphragm and cause a short circuit, and the working stability of the diaphragm is improved.
- the molar content N1 of the lithium supplement and the molar content N2 of the additive (A) satisfy the relational formula: 0.1 ⁇ N2/(N1 ⁇ m ⁇ x1) ⁇ 0.5; alternatively, N1 and N2 satisfy the relational formula: 0.27 ⁇ N2/(N1 ⁇ m ⁇ x1) ⁇ 0.35. In this way, the side reactions caused by the migration of lithium ions of the lithium-supplementing agent can be minimized, and the utilization efficiency of the lithium-supplementing agent can be further improved.
- the above-mentioned nitrone derivative having a structure represented by formula (II) in the molecule is a compound represented by the following general formula (II'), or a cyclic nitrone derivative having a 4-8 membered ring.
- R and R are independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, fluoromethyl, fluoroethyl, fluoropropyl, methylhydroxy, ethylhydroxy, phenyl, tolyl, fluorophenyl, methoxy, and ethoxy, 1,1-dimethyl-ethanol, 1,1-dimethyl-propanol, 1,1-dimethyl-butanol, 1-methyl-propanol, tert-butyl tri at least one of the alcohol groups.
- the additive (A) is at least one selected from the following N-tert-butyl- ⁇ -phenylnitrone, N-tert-butyl- ⁇ -4-fluorophenylnitrone, 5,5-dimethyl-1-pyrroline oxide, N-tert-butyl- ⁇ -methylnitrone, 2,2,6,6-tetramethylpiperidine oxide, and 4-ethoxy-2,2,6,6-tetramethylpiperidine 1-oxide.
- the thermal shrinkage rate of the separator can be reduced, and the working stability of the separator can be improved, but also the utilization efficiency of the lithium supplement added in the secondary battery can be improved, thereby improving the charge and discharge capacity, service life and safety performance of the secondary battery.
- Additive (A1) N-tert-butyl- ⁇ -phenylnitrone, the molecular formula is as follows.
- Additive (A4) N-tert-butyl- ⁇ -methylnitrone, the molecular formula is as follows.
- the additive (A) is applied to at least one side of the separator substrate close to the positive electrode (refer to (A) of FIG. 1 ), optionally, the additive (A) is applied to both sides of the separator substrate (refer to FIG. 1 (B)).
- the effect of the additive (A) on improving the utilization efficiency of the lithium supplementing agent can be further enhanced, and the flexibility of the separator can be further improved.
- the first delithiation capacity of the lithium supplement additive is 300-1500mAh/g, preferably 400-900mAh/g.
- Its first charge and discharge voltage range is 2.0-4.5V (vs Li), in order to match the corresponding potential of the positive electrode active material, the voltage range is preferably 3.0-3.75V (vs Li).
- the lithium-supplementing agent is coated on at least one side of the separator substrate close to the positive electrode, and optionally, the lithium-supplementing agent is coated on both sides of the separator substrate.
- the lithium-supplementing agent coated on the separator substrate may leave some oxides after detachment. These oxides, like nano-alumina, have poor conductivity, but can reduce the thermal shrinkage rate of the separator and improve the thermal safety performance of the secondary battery cell.
- the thickness of the separator is 3 ⁇ m-20 ⁇ m, optionally 9 ⁇ m-16 ⁇ m. Thereby, it is possible to simultaneously improve the barrier ability to electrons, the conductivity to lithium ions, and the strength of the separator.
- the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, the positive electrode film layer includes a positive electrode active material, and optionally, the positive electrode film layer also includes a lithium supplementing agent represented by the above general formula (I).
- a metal foil or a composite current collector can be used as the positive electrode current collector.
- aluminum foil can be used as the metal foil.
- the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
- the composite current collector can be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE) and the like).
- PP polypropylene
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PS polystyrene
- PE polyethylene
- the negative electrode film layer may also optionally include a conductive agent.
- the conductive agent can be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
- the negative electrode film layer may optionally include other additives, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
- thickeners such as sodium carboxymethylcellulose (CMC-Na)
- CMC-Na sodium carboxymethylcellulose
- LiFePO 4 (volume average particle size of 1.2 ⁇ m), conductive agent acetylene black, and binder (PVDF polyvinylidene fluoride) in a weight ratio of 97:1:2 to N-methylpyrrolidone (NMP) solvent. After fully stirring and mixing evenly, the surface density is 19.4 mg/cm 2 coated on Al foil, dried, cold-pressed, and the compacted density is 2.4 g/cm 3 to obtain a positive electrode sheet.
- LFP volume average particle size of 1.2 ⁇ m
- PVDF polyvinylidene fluoride binder
- NMP N-methylpyrrolidone
- the additive (A) shown in Table 1: the value of the lithium supplement agent the molar content N2/(the molar content N1 ⁇ 2.5 ⁇ 2 of the lithium supplement agent) of the additive (A).
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Abstract
Description
Claims (20)
- 一种二次电池,其中,包括正极极片、负极极片、隔膜和电解液,所述二次电池中含有补锂剂,所述补锂剂为选自下述通式(I)所表示的物质中的至少一种,mLi x1O·n(Ni y1Mn y2Co y3Cu y4Fe y5)O (I)通式(I)中,1≤x1≤2;0≤y1≤1;0≤y2≤1;0≤y3≤1;0≤y4≤2;0≤y5≤1;0.5≤y1+y2+y3+y4+y5≤1;1≤m≤3;0≤n/m≤1,且所述隔膜中包括隔膜基体以及添加剂(A),所述添加剂(A)为选自分子内具有下述式(II)所表示的结构的硝酮类衍生物或者以及分子内具有下述式(III)所表示的结构的哌啶类衍生物中的任意一种或两种以上,
- 根据权利要求1所述的二次电池,其中,所述补锂剂的摩尔含量N1和所述添加剂(A)的摩尔含量N2满足关系式:0.1≤N2/(N1×m×x1)≤0.5;可选地,N1和N2满足关系式:0.27≤N2/(N1×m×x1)≤0.35。
- 根据权利要求1或2所述的二次电池,其中,所述补锂剂为选自Li 2O、Li 2O 2、Li 5FeO 4、以及Li 2Cu 0.5Ni 0.5O 2中 的至少一种;可选地,所述补锂剂为选自Li 2O,Li 2O 2中的至少一种。
- 根据权利要求1-4中任一项所述的二次电池,其中,所述添加剂(A)为选自N-叔丁基-α-苯基硝酮、N-叔丁基-α-4-氟代苯基硝酮、5,5-二甲基-1-氧化吡咯啉、N-叔丁基-α-甲基硝酮、2,2,6,6-四甲基氧化哌啶、以及4-乙氧基-2,2,6,6-四甲基哌啶1-氧化物中的至少一种。
- 根据权利要求1-5中任一项所述的二次电池,其中,所述补锂剂的比表面积为0.5m 2/g-20m 2/g,可选为1m 2/g-2m 2/g。
- 根据权利要求1-6中任一项所述的二次电池,其中,所述添加剂(A)被涂敷于所述隔膜基体的至少靠正极一侧,可选地,所述添加剂(A)被涂敷于所述隔膜基体的两侧。
- 根据权利要求1-7中任一项所述的二次电池,其中,所述补锂剂添加于所述正极极片上的正极材料中。
- 根据权利要求1-8中任一项所述的二次电池,其中,所述添加剂(A)与纳米氧化铝混合后涂敷于隔膜基体。
- 根据权利要求1-9中任一项所述的二次电池,其中,所述补锂剂被涂敷于所述隔膜基体的至少靠正极一侧,可选地,所述补锂剂被涂敷于所述隔膜基体的两侧。
- 根据权利要求10所述的二次电池,其中,所述添加剂(A)与所述补锂剂混合后涂敷于所述隔膜基体。
- 根据权利要求10所述的二次电池,其中,在所述隔膜基体上涂敷所述补锂剂形成补锂剂层,再在所述补锂剂层之上涂敷所述添加剂(A)。
- 根据权利要求1-12中任一项所述的二次电池,其中,所述补锂剂的纯度大于等于90%;可选为大于等于95%。
- 根据权利要求1-13中任一项所述的二次电池,其中,所述补锂剂的首次脱锂容量为300-1500mAh/g,可选为400-900mAh/g。
- 根据权利要求1-14中任一项所述的二次电池,其中,所述补锂剂的首次充放电电压范围为2.0V-4.5V,可选为3.0V-3.75V。
- 根据权利要求1-15中任一项所述的二次电池,其中,所述隔膜基体由选自聚烯烃膜、聚酯膜、纤维素膜、聚酰亚胺膜、无纺布隔膜、以及聚酰亚胺薄膜中的一种或多种组合的材料形成,可选为由选自聚乙烯薄膜、聚丙烯薄膜、聚对苯二甲酸二醇酯膜、 纤维素膜、聚酰亚胺膜、无纺布隔膜、以及聚酰亚胺薄膜中的一种或多种组合的材料形成,进一步可选为由聚丙烯薄膜形成。
- 根据权利要求1-16中任一项所述的二次电池,其中,所述隔膜的厚度为3μm-20μm,可选为9μm-16μm。
- 一种电池模块,其特征在于,包括权利要求1~17中任一项所述的二次电池。
- 一种电池包,其特征在于,包括权利要求18所述的电池模块。
- 一种用电装置,其特征在于,包括选自权利要求1~17中任一项所述的二次电池、权利要求18所述的电池模块或权利要求19所述的电池包中的至少一种。
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