WO2024065181A1 - Negative electrode composition and preparation method therefor, negative electrode slurry and preparation method therefor, negative electrode sheet and preparation method therefor, secondary battery, electric device, and use of thianthrene compound - Google Patents
Negative electrode composition and preparation method therefor, negative electrode slurry and preparation method therefor, negative electrode sheet and preparation method therefor, secondary battery, electric device, and use of thianthrene compound Download PDFInfo
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- WO2024065181A1 WO2024065181A1 PCT/CN2022/121750 CN2022121750W WO2024065181A1 WO 2024065181 A1 WO2024065181 A1 WO 2024065181A1 CN 2022121750 W CN2022121750 W CN 2022121750W WO 2024065181 A1 WO2024065181 A1 WO 2024065181A1
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- WIPO (PCT)
- Prior art keywords
- negative electrode
- thianthrene
- active
- thianthrene compound
- compound
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- -1 thianthrene compound Chemical class 0.000 title claims abstract description 116
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims description 40
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- 239000011149 active material Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000005029 thianthrenes Chemical class 0.000 claims description 10
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 claims description 9
- GATVHFQKUCJQGI-UHFFFAOYSA-N 1-(7-acetylthianthren-2-yl)ethanone Chemical compound CC(=O)C1=CC=C2SC3=CC(C(=O)C)=CC=C3SC2=C1 GATVHFQKUCJQGI-UHFFFAOYSA-N 0.000 claims description 8
- XLKTXBRNWCHYAS-UHFFFAOYSA-N 1-thianthren-2-ylethanone Chemical compound C1=CC=C2SC3=CC(C(=O)C)=CC=C3SC2=C1 XLKTXBRNWCHYAS-UHFFFAOYSA-N 0.000 claims description 8
- QOGDMHZMYYSFPP-UHFFFAOYSA-N 2,7-dibromothianthrene Chemical compound BrC1=CC=C2SC3=CC(Br)=CC=C3SC2=C1 QOGDMHZMYYSFPP-UHFFFAOYSA-N 0.000 claims description 8
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- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 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
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 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
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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
Definitions
- the present application relates to the field of secondary batteries, and specifically to a negative electrode composition and a preparation method thereof, a negative electrode slurry and a preparation method thereof, a negative electrode sheet and a preparation method thereof, a secondary battery, an electrical device, and applications of thianthrene compounds.
- the negative electrode sheet of a secondary battery often has a certain porosity, which helps the electrolyte to infiltrate the negative electrode sheet to maintain the performance of the secondary battery. Therefore, how to improve the porosity of the negative electrode sheet has an important impact on the performance of the secondary battery.
- the present application provides a negative electrode composition and preparation method, a negative electrode slurry and preparation method, a negative electrode plate and preparation method, a secondary battery, an electrical device and application of thianthrene compounds.
- the negative electrode composition can effectively improve the porosity of the negative electrode plate.
- the first aspect of the present application provides a negative electrode composition.
- the negative electrode composition comprises a negative electrode active material and a thianthrene compound.
- the negative electrode composition in the present application includes thianthrene compounds. Introducing thianthrene compounds into the negative electrode composition provides a new idea for improving the porosity of the negative electrode plate, which can improve the porosity of the negative electrode plate, thereby improving the wettability of the electrolyte in the battery to the negative electrode plate and improving the performance of the battery.
- the thianthrene compound has a structure as shown in formula (I):
- R1 and R2 are independently selected from H, D, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms.
- the thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene.
- the melting point of the thianthrene compound at standard atmospheric pressure is greater than 100°C.
- the mass percentage of the thianthrene compound is ⁇ 5% based on the mass percentage of the negative electrode active material.
- the mass percentage of the thianthrene compound is 1% to 5% based on the mass percentage of the negative electrode active material.
- the D50 of the thianthrene compound is 0.5 ⁇ m to 5 ⁇ m.
- the second aspect of the present application provides a method for preparing the negative electrode composition of the first aspect, comprising the following steps: mixing the negative electrode active material and the thianthrene compound.
- the third aspect of the present application provides a negative electrode slurry, comprising a solvent and the negative electrode composition described in the first aspect.
- the fourth aspect of the present application provides a method for preparing the negative electrode slurry according to the second aspect, comprising the following steps:
- the solvent and the negative electrode composition are mixed.
- a fifth aspect of the present application provides a negative electrode sheet, comprising:
- a negative electrode active layer is disposed on at least one surface of the negative electrode current collector, and the negative electrode active layer comprises the negative electrode composition of the first aspect.
- the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is located on at least one surface of the negative electrode current collector, and the second active sublayer is located on the first active sublayer; the negative electrode composition is located in the second active sublayer.
- the mass percentage of the thianthrene compound is ⁇ 5% based on the mass percentage of the active material of the second active sub-layer.
- the mass percentage of the thianthrene compound is 1% to 5% based on the mass percentage of the active material of the second active sub-layer.
- the sixth aspect of the present application provides a method for preparing the negative electrode sheet according to the fifth aspect, comprising the following steps:
- the negative electrode active layer is formed on at least one surface of the negative electrode current collector using the negative electrode slurry described in the third aspect.
- the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is formed on at least one surface of the current collector, and the second active sublayer is formed on the first active sublayer using the negative electrode slurry.
- the seventh aspect of the present application provides an application of a thianthrene compound as a pore former in a negative electrode slurry or a negative electrode sheet.
- the thianthrene compound has a structure as shown in formula (I):
- R1 and R2 are independently selected from H, D, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms.
- the thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene.
- the melting point of the thianthrene compound at standard atmospheric pressure is greater than 100°C.
- the present application provides a secondary battery, comprising the negative electrode sheet described in the fourth aspect.
- the solvent of the electrolyte includes one or both of dimethyl carbonate and diethyl carbonate.
- a ninth aspect of the present application provides an electrical device, comprising the secondary battery described in the eighth aspect.
- FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
- FIG. 2 is an exploded view of the secondary battery according to one embodiment of the present application shown in FIG. 1 .
- FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
- FIG. 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
- FIG. 5 is an exploded view of the battery pack shown in FIG. 4 according to an embodiment of the present application.
- FIG. 6 is a schematic diagram of an electrical device using a secondary battery as a power source according to an embodiment of the present application.
- range disclosed in this application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range.
- the range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that the range of 60 to 110 and 80 to 120 is also expected.
- the numerical range "a to b" represents an abbreviation of any real number combination between a and b, where a and b are both real numbers.
- the numerical range "0 to 5" means that all real numbers between "0 to 5" have been fully listed in this article, and "0 to 5" is just an abbreviation of these numerical combinations.
- a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
- the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
- the method may further include step (c), which means that step (c) may be added to the method in any order.
- the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
- the “include” and “comprising” mentioned in this application are open-ended or closed-ended.
- the “include” and “comprising” may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
- the term "or” is inclusive.
- the phrase “A or B” means “A, B, or both A and B”. More specifically, any of the following conditions satisfies the condition "A or B”: 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 present application provides a negative electrode composition.
- the negative electrode composition includes a negative electrode active material and a thianthrene compound. Introducing the thianthrene compound into the negative electrode composition provides a new idea for improving the porosity of the negative electrode sheet, which can improve the porosity of the negative electrode sheet, thereby improving the wettability of the electrolyte in the battery to the negative electrode sheet and improving the performance of the battery.
- the negative electrode composition includes a pore former, and the pore former includes a thianthrene compound.
- the thianthrene compound is used as a pore former in the negative electrode composition.
- the traditional way to improve the porosity of the negative electrode sheet is to add a pore former to the negative electrode slurry, then coat the negative electrode slurry on the current collector, and then dry it.
- the pore former volatilizes or decomposes, leaving pores in the negative electrode active layer, thereby achieving the effect of improving the porosity of the negative electrode sheet.
- this porosity improvement method is prone to pore former residues, which in turn has an adverse effect on the performance of the battery.
- the negative electrode composition can be added to the negative electrode slurry or the negative electrode active layer, so that after the negative electrode active layer is formed, the thianthrene compound is preserved in the negative electrode active layer, and then when the negative electrode sheet is in contact with the electrolyte, the thianthrene compound gradually dissolves in the electrolyte, thereby leaving pores in the negative electrode active layer, thereby achieving the effect of improving the porosity of the negative electrode sheet.
- the thianthrene compound can be continuously dissolved in the electrolyte. Compared with the traditional method of removing the pore former by drying, the residual probability and residual amount of the pore former will be greatly reduced, thereby effectively avoiding the adverse effects of the residual pore former on battery performance.
- the volatilization or decomposition speed of the pore former at different positions in the negative electrode active layer is different.
- the outer layer of the negative electrode active layer may be heated more obviously than the inner layer, which will cause the outer layer of the negative electrode active layer to be heated faster than the inner layer.
- the problem of uneven heating of the pore former in the outer layer and the pore former in the inner layer of the negative electrode active layer is likely to occur.
- the pore former in the outer layer is heated faster than the inner layer, which will cause the pore former in the outer layer to decompose or volatilize faster than the pore former in the inner layer, resulting in uneven pores in the negative electrode active layer.
- the thianthrene compound can be slowly dissolved in the electrolyte, and the dissolution rate of the thianthrene compound in the outer layer of the negative electrode active layer is comparable to that of the thianthrene compound in the inner layer, which can improve the uniformity of the pores of the negative electrode sheet.
- the flow direction and flow mode of the gas generated by the volatilization or decomposition of the pore-forming agent are difficult to control, which can easily cause impact on the surface of the negative electrode plate, causing the surface of the negative electrode plate to be uneven, and adversely affecting the surface morphology of the negative electrode plate.
- the thianthrene compound slowly dissolves with the electrolyte, which can effectively avoid the impact of the pore-forming process on the surface of the negative electrode plate, avoid adversely affecting the surface morphology of the negative electrode plate, and help maintain the surface flatness of the negative electrode plate, thereby improving the performance of the battery.
- the dissolved thianthrene compound in the method of improving the porosity of the negative electrode sheet of the present application, can be used as an anti-overcharge additive to avoid the continuous increase of the battery voltage when overcharging occurs, thereby further improving the performance of the battery.
- the thianthrene compound has a structure as shown in formula (I):
- R1 and R2 are independently selected from H, D, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms.
- alkyl group can be a straight chain alkyl group or a branched chain alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, etc.
- the acyl group can be a straight chain acyl group or a branched chain acyl group, such as formyl, acetyl, propionyl, butyryl, isopropionyl, isobutyryl, etc.
- the thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene, and 2,7-diisobutyrylthianthrene.
- thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene have the following structural formulas, respectively:
- the melting point of the thianthrene compound at standard atmospheric pressure is greater than 100° C.
- the mass percentage of the thianthrene compound is ⁇ 5% in terms of the mass percentage of the negative electrode active material.
- the mass percentage of the thianthrene compound within this range can better balance the improvement of porosity and battery capacity.
- the mass percentage of the thianthrene compound is too large, the amount of negative electrode active material may be reduced, resulting in a decrease in battery capacity.
- the mass percentage of the thianthrene compound is ⁇ 1 in terms of the mass percentage of the negative electrode active material.
- the mass percentage of the thianthrene compound is 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% in terms of the mass percentage of the negative electrode active material.
- the mass percentage of the thianthrene compound in terms of the mass percentage of the negative electrode active material can also be selected in other suitable ranges within the range of 1% to 5%. When the mass percentage of the thianthrene compound is too large, the bonding of the negative electrode sheet may also be reduced.
- the D50 of the thianthrene compound is 0.5 ⁇ m to 5 ⁇ m.
- the D50 of the thianthrene compound can be, but is not limited to, 0.8 ⁇ m, 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, etc. It is understood that the D50 of the thianthrene compound can also be other suitable selections within the range of 0.5 ⁇ m to 5 ⁇ m.
- the present application also provides a method for preparing the above negative electrode composition, which comprises the following steps: mixing the active material and the thianthrene compound.
- the present application also provides a negative electrode slurry.
- the negative electrode slurry includes a solvent and the above-mentioned negative electrode composition.
- the negative electrode slurry includes the above-mentioned negative electrode composition.
- the negative electrode slurry further includes a binder.
- the present application also provides a method for preparing the above-mentioned negative electrode slurry, comprising the following steps: mixing a solvent and a negative electrode composition.
- the present application also provides a negative electrode plate, which includes a negative electrode current collector and a negative electrode active layer, wherein the negative electrode active layer is disposed on at least one surface of the negative electrode current collector, and the negative electrode active layer includes the negative electrode composition.
- the mass percentage of the thianthrene compound is ⁇ 5% based on the mass percentage of the negative electrode active material.
- the mass percentage of the thianthrene compound can better balance the improvement of porosity and battery capacity within this range.
- the mass percentage of the thianthrene compound is too large, the amount of the negative electrode active material may be reduced, resulting in a decrease in battery capacity.
- the mass percentage of the thianthrene compound is ⁇ 1 based on the mass percentage of the negative electrode active material.
- the mass percentage of the thianthrene compound is 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% based on the mass percentage of the negative electrode active material. It is understandable that the mass percentage of the thianthrene compound can also be selected in the range of 1% to 5% based on the mass percentage of the negative electrode active material.
- the D50 of the thianthrene compound is 0.5 ⁇ m to 5 ⁇ m.
- the D50 of the thianthrene compound can be, but is not limited to, 0.8 ⁇ m, 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, etc. It is understood that the D50 of the thianthrene compound can also be other suitable selections within the range of 0.5 ⁇ m to 5 ⁇ m.
- the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is located on at least one surface of the negative electrode current collector, and the second active sublayer is located on the first active sublayer; the negative electrode composition is located in the second active sublayer.
- the active material of the first active sublayer and the active material of the second active sublayer may be the same or different.
- the active material of the first active sublayer includes an energy-type active material
- the active material of the second active sublayer includes a power-type active material.
- the active material of the first active sublayer is energy-type graphite
- the active material of the second active sublayer is fast-charging graphite.
- the mass percentage of the thianthrene compound is ⁇ 5% based on the mass percentage of the active material in the second active sublayer.
- the mass percentage of the thianthrene compound within this range can better balance the improvement of porosity and battery capacity.
- the mass percentage of the thianthrene compound is ⁇ 1 based on the mass percentage of the active material in the second active sublayer.
- the mass percentage of the thianthrene compound is 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% based on the mass percentage of the active material in the second active sublayer. It is understandable that the mass percentage of the thianthrene compound can also be selected in the range of 1% to 5% based on the mass percentage of the active material in the second active sublayer.
- the present application also provides a method for preparing the above-mentioned negative electrode sheet, comprising the following steps: forming the negative electrode active layer on at least one surface of the negative electrode current collector using the above-mentioned negative electrode slurry.
- the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is formed on at least one surface of the current collector, and the second active sublayer is formed on the first active sublayer using the above negative electrode slurry.
- forming the first active sublayer on at least one surface of the current collector is forming the first active sublayer by slurry.
- the slurry for forming the first active sublayer does not contain the negative electrode composition.
- the present application also provides an application of a thianthrene compound as a pore former in a negative electrode slurry or a negative electrode sheet.
- the thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene.
- the melting point of the thianthrene compound at standard atmospheric pressure is greater than 100°C.
- the present application also provides a secondary battery, comprising the above-mentioned negative electrode plate and an electrolyte, wherein the negative electrode active layer of the negative electrode plate is in contact with the electrolyte.
- the secondary battery is suitable for various electrical devices using batteries, such as mobile phones, portable devices, laptop computers, battery cars, electric toys, electric tools, electric cars, ships and spacecraft, etc.
- the spacecraft includes airplanes, rockets, space shuttles and spacecrafts, etc.
- thianthrene compounds have good solubility in electrolyte.
- the solvent of the electrolyte includes one or both of dimethyl carbonate and diethyl carbonate.
- the present application also provides an electrical device, comprising the above-mentioned secondary battery.
- a secondary battery includes a positive electrode sheet, a negative electrode sheet, an electrolyte and a separator.
- active ions are embedded and released back and forth between the positive electrode sheet and the negative electrode sheet.
- the electrolyte plays the role of conducting ions between the positive electrode sheet and the negative electrode sheet.
- the separator is set between the positive electrode sheet and the negative electrode sheet, mainly to prevent the positive and negative electrodes from short-circuiting, while allowing ions to pass through.
- 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, wherein the positive electrode film layer includes a positive electrode active material.
- the positive electrode current collector has two surfaces facing each other in its thickness direction, and the positive electrode active material layer is disposed on any one or both of the two facing surfaces of the positive electrode current collector.
- the positive electrode current collector may be a metal foil or a composite current collector.
- aluminum foil may 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 may 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 a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
- PP polypropylene
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PS polystyrene
- PE polyethylene
- the positive electrode active material may include a positive electrode active material for a battery known in the art.
- the positive electrode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
- the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more.
- lithium transition metal oxides may include, but are not limited to , lithium cobalt oxide (such as LiCoO2 ), lithium nickel oxide (such as LiNiO2 ), lithium manganese oxide (such as LiMnO2 , LiMn2O4 ), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi1 / 3Co1 / 3Mn1 / 3O2 (also referred to as NCM333 ), LiNi0.5Co0.2Mn0.3O2 (also referred to as NCM523 ) , LiNi0.5Co0.25Mn0.25O2 (also referred to as NCM211 ) , LiNi0.6Co0.2Mn0.2O2 (also referred to as NCM622 ), LiNi0.8Co0.1Mn0.1O2 (also referred to as NCM811 ), lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co 0.15 Al 0.05
- lithium-containing phosphates with an olivine structure may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
- the weight ratio of the positive electrode active material in the positive electrode film layer is 80 to 100 weight %, based on the total weight of the positive electrode film layer.
- the positive electrode film layer may also optionally include a binder.
- 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 fluorine-containing acrylate resin.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PTFE polytetrafluoroethylene
- the weight ratio of the binder in the positive electrode film layer is 0 to 20% by weight, based on the total weight of the positive electrode film layer.
- the positive electrode film layer may further include a conductive agent.
- 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.
- the weight ratio of the conductive agent in the positive electrode film layer is 0 to 20 weight %, based on the total weight of the positive electrode film layer.
- the positive electrode sheet can be prepared by the following method: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry, wherein the positive electrode slurry has a solid content of 40 to 80 wt%, and the viscosity at room temperature is adjusted to 5000 to 25000 mPa ⁇ s, the positive electrode slurry is coated on the surface of the positive current collector, and after drying, the positive electrode sheet is formed after cold pressing by a cold rolling mill; the positive electrode powder coating unit area density is 150-350 mg/m 2 , and the positive electrode sheet compaction density is 3.0-3.6 g/cm 3 , and can be optionally 3.3-3.5 g/cm 3 .
- the positive electrode sheet in the embodiment of the present application can be made by using the above-mentioned positive electrode sheet as the positive electrode sheet body and forming a solid electrolyte interface film on the surface of the positive electrode sheet body.
- the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer includes a negative electrode active material.
- the negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
- the negative electrode current collector may be a metal foil or a composite current collector.
- the metal foil copper 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 substrate.
- the composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
- PP polypropylene
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PS polystyrene
- PE polyethylene
- the negative electrode active material may adopt the negative electrode active material for the battery known in the art.
- the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material and lithium titanate.
- the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites and silicon alloys.
- the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
- the present application is not limited to these materials, and other traditional materials that can be used as negative electrode active materials for batteries can also be used. These negative electrode active materials can be used alone or in combination of two or more.
- the weight ratio of the negative electrode active material in the negative electrode film layer is 70 to 100 weight%, based on the total weight of the negative electrode film layer.
- the negative electrode film layer may further include a binder.
- the binder may be selected from at least one of 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).
- SBR styrene-butadiene rubber
- PAA polyacrylic acid
- PAAS sodium polyacrylate
- PAM polyacrylamide
- PVA polyvinyl alcohol
- SA sodium alginate
- PMAA polymethacrylic acid
- CMCS carboxymethyl chitosan
- the negative electrode film layer may further include 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.
- the weight ratio of the conductive agent in the negative electrode film layer is 0 to 20 weight %, based on the total weight of the negative electrode film layer.
- the negative electrode film layer may further include other additives, such as a thickener (such as sodium carboxymethyl cellulose (CMC-Na)), etc.
- a thickener such as sodium carboxymethyl cellulose (CMC-Na)
- the weight ratio of the other additives in the negative electrode film layer is 0 to 15 weight %, based on the total weight of the negative electrode film layer.
- the negative electrode sheet can be prepared by the following method: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as deionized water) to form a negative electrode slurry, wherein the solid content of the negative electrode slurry is 30-70wt%, and the viscosity at room temperature is adjusted to 2000-10000mPa ⁇ s; the obtained negative electrode slurry is coated on the negative electrode collector, and after a drying process, cold pressing such as rolling, a negative electrode sheet is obtained.
- the negative electrode powder coating unit area density is 75-220mg/ m2
- the negative electrode sheet compaction density is 1.2-2.0g/ m3 .
- the negative electrode sheet in the embodiment of the present application can be made by using the above-mentioned negative electrode sheet as the negative electrode sheet body and forming a solid electrolyte interface film on the surface of the negative electrode sheet body.
- the electrolyte plays the role of conducting ions between the positive electrode and the negative electrode.
- the present application has no specific restrictions on the type of electrolyte, which can be selected according to needs.
- the electrolyte can be liquid, gel or all-solid.
- the electrolyte is an electrolyte solution, which includes an electrolyte salt and a solvent.
- the electrolyte salt may be selected from one or more of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluorooxalatoborate (LiDFOB), lithium dioxalatoborate (LiBOB), lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorobis(oxalatophosphate) (LiDFOP) and lithium tetrafluorooxalatophosphate (LiTFOP).
- concentration of the electrolyte salt is generally 0.5 to
- the solvent can be selected from one or more of fluoroethylene carbonate (FEC), ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), butylene carbonate (BC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), ethyl methyl sulfone (EMS) and diethyl sulfone (FEC),
- the electrolyte may further include additives, such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
- additives such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
- the secondary battery further includes a separator.
- the present application has no particular limitation on the type of separator, and any known porous separator with good chemical stability and mechanical stability can be selected.
- the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
- the isolation membrane can be a single-layer film or a multi-layer composite film, without particular limitation.
- the materials of each layer can be the same or different, without particular limitation.
- the positive electrode sheet, the negative electrode sheet, and the separator may be formed into an electrode assembly by a winding process or a lamination process.
- the secondary battery may include an outer package, which may be used to encapsulate the electrode assembly and the electrolyte.
- the outer packaging of the secondary battery can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
- the outer packaging of the secondary battery can also be a soft package, such as a bag-type soft package.
- the material of the soft package can be plastic, and as plastic, polypropylene, polybutylene terephthalate, and polybutylene succinate can be listed.
- the present application has no particular restrictions on the shape of the secondary battery, which can be cylindrical, square, or other arbitrary shapes.
- FIG. 1 is a secondary battery 5 of a square structure as an example.
- the outer package may include a shell 51 and a cover plate 53.
- the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
- the shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity.
- the positive electrode sheet, the negative electrode sheet and the isolation film can form an electrode assembly 52 through a winding process or a lamination process.
- the electrode assembly 52 is encapsulated in the receiving cavity.
- the electrolyte is infiltrated in the electrode assembly 52.
- the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
- secondary batteries may be assembled into a battery module.
- the number of 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.
- FIG3 is a battery module 4 as an example.
- a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, they may also be arranged in any other manner. Further, the plurality of secondary batteries 5 may be fixed by fasteners.
- the battery module 4 may further include a housing having a housing space, and the plurality of secondary batteries 5 are housed in the housing space.
- the battery modules described above may also be assembled into a battery pack.
- the battery pack may contain one or more battery modules, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
- FIG4 and FIG5 are battery packs 1 as an example.
- the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
- the battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 to form a closed space for accommodating the battery modules 4.
- the plurality of battery modules 4 can be arranged in the battery box in any manner.
- the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application.
- the secondary battery, battery module, or battery pack can be used as a power source for the electrical device, and can also be used as an energy storage unit for the electrical device.
- the electrical device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
- a secondary battery, a battery module or a battery pack may be selected according to its usage requirements.
- Fig. 6 is an example of an electric device.
- the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
- a battery pack or a battery module may be used.
- a device may be a mobile phone, a tablet computer, a notebook computer, etc. Such a device is usually required to be thin and light, and a secondary battery may be used as a power source.
- CMC and deionized water were stirred for 3 hours under the condition of vacuum degree less than -0.08MPa to obtain CMC aqueous solution, and then carbon black, SBR, graphite, and thionyl compounds were added to the CMC aqueous solution, and fully stirred for 7 hours under the condition of vacuum degree less than -0.08MPa to obtain negative electrode slurry.
- the negative electrode slurry obtained in (1) is evenly coated on the surface of a copper foil with a thickness of 12 ⁇ m, and then dried at 95°C to obtain a negative electrode pre-finished product.
- LiFePO 4 lithium iron phosphate
- CB conductive carbon black
- PVDF polyvinylidene fluoride
- NMP N-methylpyrrolidone
- the negative electrode sheet, positive electrode sheet and 25 ⁇ m thick polypropylene film separator prepared in the above steps (2) and (3) are stacked in the order of positive electrode sheet, separator and negative electrode sheet, and then wound to make the electrode core of the lithium ion battery.
- the electrode core is placed in a steel square lithium ion battery shell with a height of 50 mm, a thickness of 5 mm and a width of 34 mm, and then 3.8 g of electrolyte is injected, and finally the battery shell is sealed to make a 053450 lithium ion battery.
- the electrolyte is a LiPF 6 /EC+DEC+EMC+DMC system.
- Example 2 Compared with Example 1, the difference of this example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 1 part.
- Example 2 Compared with Example 1, the difference of this example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 2 parts.
- Example 2 Compared with Example 1, the difference of this example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 4 parts.
- Example 2 Compared with Example 1, the difference of this example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 5 parts.
- the difference of this embodiment is that the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is located on at least one surface of the negative electrode current collector, and the second active sublayer is located on the first active sublayer.
- the difference between the active slurry of the first active sublayer and step (1) in Example 1 is that the negative electrode slurry does not contain thianthrene compounds, and the active slurry of the second active sublayer is the negative electrode slurry obtained in step (1) in Example 1.
- the preparation method of the negative electrode sheet in this embodiment is: the first active layer negative electrode slurry prepared above is evenly coated on the surface of a copper foil with a thickness of 12 ⁇ m, and then the second active layer negative electrode slurry prepared above is evenly coated on the first active layer negative electrode, and then the water is dried at 95°C to obtain a pre-finished negative electrode sheet.
- the difference of this example is that in the negative electrode slurry, the thianthrene compound is 2-acetylthianthrene.
- the difference of this example is that in the negative electrode slurry, the thianthrene compound is 2,7-diacetylthianthrene.
- Example 2 Compared with Example 1, the difference of this example is that in the negative electrode slurry, the thianthrene compound is 2,7-dibromothianthrene.
- the difference of this example is that in the negative electrode slurry, the thianthrene compound is 2,7-diisobutyrylthianthrene.
- Example 1 Compared with Example 1, the difference of this comparative example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 0 parts.
- Example 1 Compared with Example 1, the difference of this comparative example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 6 parts.
- Example 2 Compared with Example 1, the difference of this example is that in the negative electrode slurry, the D50 of the thianthrene compound is 0.2 ⁇ m.
- Example 1 Compared with Example 1, the difference of this comparative example is that in the negative electrode slurry, the D50 of the thianthrene compound is 10 ⁇ m.
- Example 6 Compared with Example 6, the difference of this comparative example is that a thianthrene pore former is added to the active slurry of the first active sublayer, and the second active sublayer is a negative electrode slurry without a pore former.
- the test method for the capacity of a lithium-ion battery is as follows: at 25°C, first charge the battery to 3.65V at a constant current of 1C, then charge it to a current of 0.05C at a constant voltage of 3.65V, and then discharge it to 2.5V at a constant current of 1C. This is a charge and discharge cycle process, and the discharge capacity this time is the discharge capacity of the first cycle.
- the test method for the rate performance of lithium-ion batteries is as follows: at 25°C, the battery is first charged to 3.65V at a constant current of 1C, further charged to a current of 0.05C at a constant voltage of 3.65V, and then discharged to 2.5V at a constant current of 1C.
- This is a charge and discharge cycle process, and the discharge capacity this time is the discharge capacity of the first cycle; then the battery cell is charged to 3.65V at a constant current of 1C, further charged to a current of 0.05C at a constant voltage of 3.65V, and then discharged to 2.5V at a constant current of 2C.
- This is a charge and discharge cycle process, and the discharge capacity this time is the discharge capacity of the second cycle, and the ratio of the discharge capacity of the second cycle to the discharge capacity of the first cycle is recorded as the 2C rate capacity retention rate.
- the internal resistance test method of the battery is: use a 1KHz sinusoidal current to test the voltage drop caused and calculate the internal resistance.
Abstract
Provided in the present application are a negative electrode composition and a preparation method therefor, a negative electrode slurry and a preparation method therefor, a negative electrode sheet and a preparation method therefor, a secondary battery, an electric device, and the use of a thianthrene compound. The negative electrode composition comprises a negative electrode active material and a thianthrene compound.
Description
本申请涉及二次电池领域，具体涉及一种负极组合物及制备方法、负极浆料及制备方法、负极极片及制备方法、二次电池、用电装置以及噻蒽类化合物的应用。The present application relates to the field of secondary batteries, and specifically to a negative electrode composition and a preparation method thereof, a negative electrode slurry and a preparation method thereof, a negative electrode sheet and a preparation method thereof, a secondary battery, an electrical device, and applications of thianthrene compounds.
二次电池的负极极片往往具有一定的孔隙率，这样有助于电解液对负极极片的浸润，以保持二次电池的性能。因此，如何改善负极极片的孔隙率对二次电池的性能具有重要的影响。The negative electrode sheet of a secondary battery often has a certain porosity, which helps the electrolyte to infiltrate the negative electrode sheet to maintain the performance of the secondary battery. Therefore, how to improve the porosity of the negative electrode sheet has an important impact on the performance of the secondary battery.
发明内容Summary of the invention
基于上述问题，本申请提供一种负极组合物及制备方法、负极浆料及制备方法、负极极片及制备方法、二次电池、用电装置以及噻蒽类化合物的应用，该负极组合物可以有效改善负极极片的孔隙率。Based on the above problems, the present application provides a negative electrode composition and preparation method, a negative electrode slurry and preparation method, a negative electrode plate and preparation method, a secondary battery, an electrical device and application of thianthrene compounds. The negative electrode composition can effectively improve the porosity of the negative electrode plate.
为了实现上述目的，本申请的第一方面提供了一种负极组合物。该负极组合物包括负极活性材料和噻蒽类化合物。In order to achieve the above-mentioned object, the first aspect of the present application provides a negative electrode composition. The negative electrode composition comprises a negative electrode active material and a thianthrene compound.
本申请中负极组合物包括噻蒽类化合物，将噻蒽类化合物引入到负极组合物中，为负极极片孔隙率的改善提供了一种新的思路，可以改善负极极片的孔隙率，进而改善电池中电解液对负极极片的浸润性，改善电池的性能。The negative electrode composition in the present application includes thianthrene compounds. Introducing thianthrene compounds into the negative electrode composition provides a new idea for improving the porosity of the negative electrode plate, which can improve the porosity of the negative electrode plate, thereby improving the wettability of the electrolyte in the battery to the negative electrode plate and improving the performance of the battery.
在其中一些实施例中，所述噻蒽类化合物具有如式(Ⅰ)所示的结构：In some embodiments, the thianthrene compound has a structure as shown in formula (I):
其中，R
1和R
2分别独立地选自H、D、F、Cl、Br、I、碳原子数为1～10的烷基、碳原子数为1～10的酰基。
wherein R1 and R2 are independently selected from H, D, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms.
在其中一些实施例中，所述噻蒽类化合物包括噻蒽、2-乙酰基噻蒽、2,7-二乙酰基噻蒽、2,7-二溴噻蒽以及2,7-二异丁酰基噻蒽中的一种或多种。In some embodiments, the thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene.
在其中一些实施例中，所述噻蒽类化合物在标准大气压下的熔点＞100℃。In some embodiments, the melting point of the thianthrene compound at standard atmospheric pressure is greater than 100°C.
在其中一些实施例中，以占所述负极活性材料的质量百分数计，所述噻蒽类化合物的质量百分数≤5％。In some embodiments, the mass percentage of the thianthrene compound is ≤5% based on the mass percentage of the negative electrode active material.
在其中一些实施例中，以占所述负极活性材料的质量百分数计，所述噻蒽类化合物的质量百分数为1％～5％。In some embodiments, the mass percentage of the thianthrene compound is 1% to 5% based on the mass percentage of the negative electrode active material.
在其中一些实施例中，所述噻蒽类化合物的D50为0.5μm～5μm。In some embodiments, the D50 of the thianthrene compound is 0.5 μm to 5 μm.
本申请第二方面提供提供了第一方面的负极组合物的制备方法，包括如下步骤：将所述负极活性材料和所述噻蒽类化合物混合。The second aspect of the present application provides a method for preparing the negative electrode composition of the first aspect, comprising the following steps: mixing the negative electrode active material and the thianthrene compound.
本申请第三方面提供了一种负极浆料，包括溶剂和第一方面所述的负极组合物。The third aspect of the present application provides a negative electrode slurry, comprising a solvent and the negative electrode composition described in the first aspect.
本申请第四方面提供了一种第二方面所述的负极浆料的制备方法，包括如下步骤：The fourth aspect of the present application provides a method for preparing the negative electrode slurry according to the second aspect, comprising the following steps:
将所述溶剂和所述负极组合物混合。The solvent and the negative electrode composition are mixed.
本申请第五方面提供了一种负极极片，包括：A fifth aspect of the present application provides a negative electrode sheet, comprising:
负极集流体；及Anode current collector; and
负极活性层，所述负极活性层设于所述负极集流体的至少一个表面之上，所述负极活性层包括第一方面的负极组合物。A negative electrode active layer is disposed on at least one surface of the negative electrode current collector, and the negative electrode active layer comprises the negative electrode composition of the first aspect.
在其中一些实施例中，所述负极活性层分为层叠设置的第一活性子层和第二活性子层，所述第一活性子层位于所述负极集流体的至少一个表面之上，所述第二活性子层位于所述第一活性子层之上；所述负极组合物位于所述第二活性子层。In some embodiments, the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is located on at least one surface of the negative electrode current collector, and the second active sublayer is located on the first active sublayer; the negative electrode composition is located in the second active sublayer.
在其中一些实施例中，以占所述第二活性子层的活性材料的质量百分数计，所述噻蒽类化合物的质量百分数≤5％。In some of the embodiments, the mass percentage of the thianthrene compound is ≤5% based on the mass percentage of the active material of the second active sub-layer.
在其中一些实施例中，以占所述第二活性子层的活性材料的质量百分数计，所述噻蒽类化合物的质量百分数为1％～5％。In some of the embodiments, the mass percentage of the thianthrene compound is 1% to 5% based on the mass percentage of the active material of the second active sub-layer.
本申请第六方面提供了第五方面所述的负极极片的制备方法，包括如下步骤：The sixth aspect of the present application provides a method for preparing the negative electrode sheet according to the fifth aspect, comprising the following steps:
在所述负极集流体的至少一个表面之上采用第三方面所述的负极浆料形成所述负极活性层。The negative electrode active layer is formed on at least one surface of the negative electrode current collector using the negative electrode slurry described in the third aspect.
在其中一些实施例中，所述负极活性层分为层叠设置的第一活性子层和第二活性子层，在所述集流体的至少一个表面之上形成所述第一活性子层，在所述第一活性子层之上采用所述负极浆料形成所述第二活性子层。In some embodiments, the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is formed on at least one surface of the current collector, and the second active sublayer is formed on the first active sublayer using the negative electrode slurry.
本申请第七方面提供了一种噻蒽类化合物在负极浆料或负极极片中作为造孔剂的应用。The seventh aspect of the present application provides an application of a thianthrene compound as a pore former in a negative electrode slurry or a negative electrode sheet.
在其中一些实施例中，所述噻蒽类化合物具有如式(Ⅰ)所示的结构：In some embodiments, the thianthrene compound has a structure as shown in formula (I):
其中，R
1和R
2分别独立地选自H、D、F、Cl、Br、I、碳原子数为1～10的烷基、碳原子数为1～10的酰基。
wherein R1 and R2 are independently selected from H, D, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms.
在其中一些实施例中，所述噻蒽类化合物包括噻蒽、2-乙酰基噻蒽、2,7-二乙酰基噻蒽、2,7-二溴噻蒽以及2,7-二异丁酰基噻蒽中的一种或几种。In some embodiments, the thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene.
在其中一些实施例中，所述噻蒽类化合物在标准大气压下的熔点＞100℃。In some embodiments, the melting point of the thianthrene compound at standard atmospheric pressure is greater than 100°C.
本申请第八方面提供了一种二次电池，包括第四方面所述的负极极片；及In an eighth aspect, the present application provides a secondary battery, comprising the negative electrode sheet described in the fourth aspect; and
电解液，所述负极极片的负极活性层与所述电解液接触。An electrolyte, wherein the negative electrode active layer of the negative electrode plate is in contact with the electrolyte.
在其中一些实施例中，所述电解液的溶剂包括碳酸二甲酯和碳酸二乙酯中的一种或两种。In some embodiments, the solvent of the electrolyte includes one or both of dimethyl carbonate and diethyl carbonate.
本申请第九方面提供了一种用电装置，包括第八方面所述的二次电池。A ninth aspect of the present application provides an electrical device, comprising the secondary battery described in the eighth aspect.
为了更清楚地说明本申请的技术方案，下面将对本申请中所使用的附图作简单介绍。显而易见地，下面所描述的附图仅仅是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on the drawings without creative work.
图1为本申请一实施方式的二次电池的示意图。FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
图2为图1所示的本申请一实施方式的二次电池的分解图。FIG. 2 is an exploded view of the secondary battery according to one embodiment of the present application shown in FIG. 1 .
图3为本申请一实施方式的电池模块的示意图。FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
图4为本申请一实施方式的电池包的示意图。FIG. 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
图5为图4所示的本申请一实施方式的电池包的分解图。FIG. 5 is an exploded view of the battery pack shown in FIG. 4 according to an embodiment of the present application.
图6为本申请一实施方式的二次电池用作电源的用电装置的示意图。FIG. 6 is a schematic diagram of an electrical device using a secondary battery as a power source according to an embodiment of the present application.
附图标记说明：Description of reference numerals:
1、电池包；2、上箱体；3、下箱体；4、电池模块；5、二次电池；51、壳体；52、电极组件；53、盖板；6、用电装置。1. Battery pack; 2. Upper box; 3. Lower box; 4. Battery module; 5. Secondary battery; 51. Shell; 52. Electrode assembly; 53. Cover plate; 6. Electrical device.
为了更好地描述和说明这里公开的那些发明的实施例和/或示例，可以参考一副或多副附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的任何一者的范围的限制。In order to better describe and illustrate the embodiments and/or examples of the inventions disclosed herein, reference may be made to one or more drawings. The additional details or examples used to describe the drawings should not be considered to limit the scope of the disclosed inventions, the embodiments and/or examples currently described, and any of the best modes of these inventions currently understood.
为了便于理解本申请，下面将参照相关附图对本申请进行更全面的描述。附图中给出了本申请的较佳实施例。但是，本申请可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本申请的公开内容的理解更加透彻全面。In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present application are given in the drawings. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present application belongs. The terms used herein in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The term "and/or" used herein includes any and all combinations of one or more related listed items.
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60～120和80～110的范围，理解为60～110和80～120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1～3、1～4、1～5、2～3、2～4和2～5。在本申请中，除非有其他说明，数值范围“a～b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0～5”表示本文中已经全部列出了“0～5”之间的全部实数，“0～5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。The "range" disclosed in this application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that the range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4 and 5 are listed, the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In this application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0 to 5" means that all real numbers between "0 to 5" have been fully listed in this article, and "0 to 5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。If there is no special explanation, all steps of the present application can be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或 包含列出的组分。If there is no special explanation, the "include" and "comprising" mentioned in this application are open-ended or closed-ended. For example, the "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": 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).
除非另有说明，本申请中使用的术语具有本领域技术人员通常所理解的公知含义。除非另有说明，本申请中提到的各参数的数值可以用本领域常用的各种测量方法进行测量(例如，可以按照在本申请的实施例中给出的方法进行测试)。Unless otherwise specified, the terms used in this application have the commonly known meanings generally understood by those skilled in the art. Unless otherwise specified, the numerical values of the various parameters mentioned in this application can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the examples of this application).
本申请提供了一种负极组合物。该负极组合物包括负极活性材料和噻蒽类化合物。将噻蒽类化合物引入到负极组合物中，为负极极片孔隙率的改善提供了一种新的思路，可以改善负极极片的孔隙率，进而改善电池中电解液对负极极片的浸润性，改善电池的性能。The present application provides a negative electrode composition. The negative electrode composition includes a negative electrode active material and a thianthrene compound. Introducing the thianthrene compound into the negative electrode composition provides a new idea for improving the porosity of the negative electrode sheet, which can improve the porosity of the negative electrode sheet, thereby improving the wettability of the electrolyte in the battery to the negative electrode sheet and improving the performance of the battery.
在一些实施方式中，负极组合物包括造孔剂，造孔剂包括噻蒽类化合物。此时，噻蒽类化合物在负极组合物中作为造孔剂使用。In some embodiments, the negative electrode composition includes a pore former, and the pore former includes a thianthrene compound. In this case, the thianthrene compound is used as a pore former in the negative electrode composition.
通常情况下，对于负极极片改善孔隙率的传统方式是在负极浆料中添加造孔剂，然后将负极浆料涂覆在集流体上，再进行干燥。在负极浆料的干燥过程中造孔剂挥发或者分解，进而在负极活性层中留下孔隙，达到改善负极极片孔隙率的效果。然而，由于浆料的干燥过程中通常只是进行一次性操作，因此，这一孔隙率的改善方式容易出现造孔剂残留，进而对电池的性能造成不利影响。在本申请中，可以将负极组合物加入负极浆料或负极活性层中，这样在形成负极活性层之后噻蒽类化合物保存在负极活性层中，然后当负极极片与电解液接触时，噻蒽类化合物逐渐在电解液中溶解，进而在负极活性层中留下孔隙，达到改善负极极片孔隙率的效果。在本申请的改善负极极片孔隙率的方式中，噻蒽类化合物可以在电解液中持续溶解，这样相比于传统的干燥去除造孔剂的方式，造孔剂的残留概率以及残留量会大大降低，进而可以有效避免造孔剂残留对电池性能产生的不利影响。Generally, the traditional way to improve the porosity of the negative electrode sheet is to add a pore former to the negative electrode slurry, then coat the negative electrode slurry on the current collector, and then dry it. During the drying process of the negative electrode slurry, the pore former volatilizes or decomposes, leaving pores in the negative electrode active layer, thereby achieving the effect of improving the porosity of the negative electrode sheet. However, since the drying process of the slurry is usually only a one-time operation, this porosity improvement method is prone to pore former residues, which in turn has an adverse effect on the performance of the battery. In the present application, the negative electrode composition can be added to the negative electrode slurry or the negative electrode active layer, so that after the negative electrode active layer is formed, the thianthrene compound is preserved in the negative electrode active layer, and then when the negative electrode sheet is in contact with the electrolyte, the thianthrene compound gradually dissolves in the electrolyte, thereby leaving pores in the negative electrode active layer, thereby achieving the effect of improving the porosity of the negative electrode sheet. In the method of improving the porosity of the negative electrode plate of the present application, the thianthrene compound can be continuously dissolved in the electrolyte. Compared with the traditional method of removing the pore former by drying, the residual probability and residual amount of the pore former will be greatly reduced, thereby effectively avoiding the adverse effects of the residual pore former on battery performance.
另外，在传统的干燥去除造孔剂的方式中，负极活性层中不同位置的造孔剂的挥发或者分解速度不同，比如在同一干燥环境下，负极活性层的外层受热可能会比内层受热更加明显，这样会导致负极活性层的外层受热的速度较内层更快，此时容易出现负极活性层外层的造孔剂与内层的造孔剂受热不均匀的问题，比如，外层的造孔剂受热的速度较内层更快，这样就会导致外层的造孔剂较内层的造孔剂更快地分解或挥发，导致负极活性层的孔隙不均匀。而在本申请的改善负极极片孔隙率的方式中，噻蒽类化合物可以在电解液中缓慢溶解，负极活 性层外层的噻蒽类化合物与内层的噻蒽类化合物的溶解速度相当，这样可以提高负极极片孔隙的均匀性。In addition, in the traditional method of removing the pore former by drying, the volatilization or decomposition speed of the pore former at different positions in the negative electrode active layer is different. For example, under the same drying environment, the outer layer of the negative electrode active layer may be heated more obviously than the inner layer, which will cause the outer layer of the negative electrode active layer to be heated faster than the inner layer. At this time, the problem of uneven heating of the pore former in the outer layer and the pore former in the inner layer of the negative electrode active layer is likely to occur. For example, the pore former in the outer layer is heated faster than the inner layer, which will cause the pore former in the outer layer to decompose or volatilize faster than the pore former in the inner layer, resulting in uneven pores in the negative electrode active layer. In the method of improving the porosity of the negative electrode sheet of the present application, the thianthrene compound can be slowly dissolved in the electrolyte, and the dissolution rate of the thianthrene compound in the outer layer of the negative electrode active layer is comparable to that of the thianthrene compound in the inner layer, which can improve the uniformity of the pores of the negative electrode sheet.
另外，在传统的干燥去除造孔剂的方式中，造孔剂的挥发或分解产生的气体的流动方向和流动方式难以控制，这样容易对负极极片的表面造成冲击，造成负极极片表面的凹凸不平，对负极极片的表面形貌造成不利影响。而在本申请的改善负极极片孔隙率的方式中，噻蒽类化合物随着电解液缓慢溶解，这样可以有效避免造孔过程对负极极片表面造成冲击，避免对负极极片的表面形貌造成不利影响，有利于保持负极极片的表面平整度，进而可以改善电池的性能。In addition, in the traditional method of removing the pore-forming agent by drying, the flow direction and flow mode of the gas generated by the volatilization or decomposition of the pore-forming agent are difficult to control, which can easily cause impact on the surface of the negative electrode plate, causing the surface of the negative electrode plate to be uneven, and adversely affecting the surface morphology of the negative electrode plate. In the method of improving the porosity of the negative electrode plate of the present application, the thianthrene compound slowly dissolves with the electrolyte, which can effectively avoid the impact of the pore-forming process on the surface of the negative electrode plate, avoid adversely affecting the surface morphology of the negative electrode plate, and help maintain the surface flatness of the negative electrode plate, thereby improving the performance of the battery.
另外，在本申请的改善负极极片孔隙率的方式中，噻蒽类化合物溶解于电解液之后，溶解的噻蒽类化合物可以作为防过充添加剂，在出现过充时，避免电池电压的持续升高，进一步可以改善电池的性能。In addition, in the method of improving the porosity of the negative electrode sheet of the present application, after the thianthrene compound is dissolved in the electrolyte, the dissolved thianthrene compound can be used as an anti-overcharge additive to avoid the continuous increase of the battery voltage when overcharging occurs, thereby further improving the performance of the battery.
在一些实施方式中，噻蒽类化合物具有如式(Ⅰ)所示的结构：In some embodiments, the thianthrene compound has a structure as shown in formula (I):
其中，R
1和R
2分别独立地选自H、D、F、Cl、Br、I、碳原子数为1～10的烷基、碳原子数为1～10的酰基。
wherein R1 and R2 are independently selected from H, D, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms.
可以理解的是，烷基可以是直链烷基或支链烷基，比如甲基、乙基、丙基、丁基、异丙基、异丁基等。酰基可以是直链酰基或支链酰基，比如甲酰基、乙酰基、丙酰基、丁酰基、异丙酰基、异丁酰基等。It is understood that the alkyl group can be a straight chain alkyl group or a branched chain alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, etc. The acyl group can be a straight chain acyl group or a branched chain acyl group, such as formyl, acetyl, propionyl, butyryl, isopropionyl, isobutyryl, etc.
在一些实施方式中，噻蒽类化合物包括噻蒽、2-乙酰基噻蒽、2,7-二乙酰基噻蒽、2,7-二溴噻蒽以及2,7-二异丁酰基噻蒽中的一种或多种。In some embodiments, the thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene, and 2,7-diisobutyrylthianthrene.
对应地，噻蒽、2-乙酰基噻蒽、2,7-二乙酰基噻蒽、2,7-二溴噻蒽以及2,7-二异丁酰基噻蒽分别具有如下结构式：Correspondingly, thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene have the following structural formulas, respectively:
在一些实施方式中，噻蒽类化合物在标准大气压下的熔点＞100℃。此时，当将噻蒽类化合物应用到负极浆料并涂覆到集流体上进行干燥时，噻蒽类化合物不易气化和挥发，可以进一步降低造孔时对负极极片表面平整度带来的不利影响。In some embodiments, the melting point of the thianthrene compound at standard atmospheric pressure is greater than 100° C. At this time, when the thianthrene compound is applied to the negative electrode slurry and coated on the current collector for drying, the thianthrene compound is not easy to gasify and volatilize, which can further reduce the adverse effect on the surface flatness of the negative electrode sheet during pore formation.
在一些实施方式中，以占负极活性材料的质量百分数计，噻蒽类化合物的质量百分数≤5％。噻蒽类化合物的质量百分数在该范围内可以较好地兼顾改善孔隙率和电池容量。当噻蒽类化合物的质量百分数过大时，可能会降低负极活性材料的用量，导致电池容量降低。可选地，以占负极活性材料的质量百分数计，噻蒽类化合物的质量百分数≥1。比如，以占负极活性材料的质量百分数计，噻蒽类化合物的质量百分数为1.5％、2％、2.5％、3％、3.5％、4％、4.5％或5％等。可以理解的是，以占负极活性材料的质量百分数计，噻蒽类化合物的质量百分数还可以在1％～5％范围内进行其他合适的选择。当噻蒽类化合物的质量百分数过大时，还可能会是负极极片的粘结性降低，In some embodiments, the mass percentage of the thianthrene compound is ≤5% in terms of the mass percentage of the negative electrode active material. The mass percentage of the thianthrene compound within this range can better balance the improvement of porosity and battery capacity. When the mass percentage of the thianthrene compound is too large, the amount of negative electrode active material may be reduced, resulting in a decrease in battery capacity. Optionally, the mass percentage of the thianthrene compound is ≥1 in terms of the mass percentage of the negative electrode active material. For example, the mass percentage of the thianthrene compound is 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% in terms of the mass percentage of the negative electrode active material. It is understandable that the mass percentage of the thianthrene compound in terms of the mass percentage of the negative electrode active material can also be selected in other suitable ranges within the range of 1% to 5%. When the mass percentage of the thianthrene compound is too large, the bonding of the negative electrode sheet may also be reduced.
在一些实施方式中，噻蒽类化合物的D50为0.5μm～5μm。可选地，噻蒽类化合物的D50可以是但不限定为0.8μm、1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、4μm、4.5μm等。可以理解的是，噻蒽类化合物的D50还可以在0.5μm～5μm范围内做其他合适的选择。In some embodiments, the D50 of the thianthrene compound is 0.5 μm to 5 μm. Alternatively, the D50 of the thianthrene compound can be, but is not limited to, 0.8 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, etc. It is understood that the D50 of the thianthrene compound can also be other suitable selections within the range of 0.5 μm to 5 μm.
本申请还提供了一种上述负极组合物的制备方法。该制备方法包括如下步骤：将活性材料和噻蒽类化合物混合。The present application also provides a method for preparing the above negative electrode composition, which comprises the following steps: mixing the active material and the thianthrene compound.
本申请还提供了一种负极浆料。该负极浆料包括溶剂和上述负极组合物。该负极浆料包括上述负极组合物，通过该负极浆料制备电池时，可以有效改善负极极片的孔隙率，并且孔隙均匀性较好，同时可以使负极极片的表面保持良好的平整性。另外，在电池中，该负极组合物中的噻蒽类化合物的溶解之后可以作为防过充添加剂，有利于进一步改善电池的性能。The present application also provides a negative electrode slurry. The negative electrode slurry includes a solvent and the above-mentioned negative electrode composition. The negative electrode slurry includes the above-mentioned negative electrode composition. When the battery is prepared by the negative electrode slurry, the porosity of the negative electrode sheet can be effectively improved, and the pore uniformity is good, and the surface of the negative electrode sheet can be kept smooth. In addition, in the battery, the thianthrene compound in the negative electrode composition can be used as an anti-overcharge additive after dissolution, which is conducive to further improving the performance of the battery.
在一些实施方式中，负极浆料还包括粘结剂。In some embodiments, the negative electrode slurry further includes a binder.
本申请还提供了一种上述负极浆料的制备方法，包括如下步骤：将溶剂和负极组合物混合。The present application also provides a method for preparing the above-mentioned negative electrode slurry, comprising the following steps: mixing a solvent and a negative electrode composition.
本申请还提供了一种负极极片。该负极极片包括负极集流体；及负极活性层，负极活性层设于负极集流体的至少一个表面之上，负极活性层包括上述负极组合物。The present application also provides a negative electrode plate, which includes a negative electrode current collector and a negative electrode active layer, wherein the negative electrode active layer is disposed on at least one surface of the negative electrode current collector, and the negative electrode active layer includes the negative electrode composition.
在一些实施方式中，以占负极活性材料的质量百分数计，噻蒽类化合物的质量百分数≤ 5％。噻蒽类化合物的质量百分数在该范围内可以较好地兼顾改善孔隙率和电池容量。当噻蒽类化合物的质量百分数过大时，可能会降低负极活性材料的用量，导致电池容量降低。可选地，以占负极活性材料的质量百分数计，噻蒽类化合物的质量百分数≥1。比如，以占负极活性材料的质量百分数计，噻蒽类化合物的质量百分数为1.5％、2％、2.5％、3％、3.5％、4％、4.5％或5％等。可以理解的是，以占负极活性材料的质量百分数计，噻蒽类化合物的质量百分数还可以在1％～5％范围内进行其他合适的选择。In some embodiments, the mass percentage of the thianthrene compound is ≤ 5% based on the mass percentage of the negative electrode active material. The mass percentage of the thianthrene compound can better balance the improvement of porosity and battery capacity within this range. When the mass percentage of the thianthrene compound is too large, the amount of the negative electrode active material may be reduced, resulting in a decrease in battery capacity. Optionally, the mass percentage of the thianthrene compound is ≥ 1 based on the mass percentage of the negative electrode active material. For example, the mass percentage of the thianthrene compound is 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% based on the mass percentage of the negative electrode active material. It is understandable that the mass percentage of the thianthrene compound can also be selected in the range of 1% to 5% based on the mass percentage of the negative electrode active material.
在一些实施方式中，噻蒽类化合物的D50为0.5μm～5μm。可选地，噻蒽类化合物的D50可以是但不限定为0.8μm、1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、4μm、4.5μm等。可以理解的是，噻蒽类化合物的D50还可以在0.5μm～5μm范围内做其他合适的选择。In some embodiments, the D50 of the thianthrene compound is 0.5 μm to 5 μm. Alternatively, the D50 of the thianthrene compound can be, but is not limited to, 0.8 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, etc. It is understood that the D50 of the thianthrene compound can also be other suitable selections within the range of 0.5 μm to 5 μm.
在一些实施方式中，负极活性层分为层叠设置的第一活性子层和第二活性子层，第一活性子层位于负极集流体的至少一个表面之上，第二活性子层位于第一活性子层之上；负极组合物位于第二活性子层。In some embodiments, the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is located on at least one surface of the negative electrode current collector, and the second active sublayer is located on the first active sublayer; the negative electrode composition is located in the second active sublayer.
可选地，第一活性子层的活性材料和第二活性子层的活性材料可以相同或不同。可选地，第一活性子层的活性材料包括能量型的活性材料，第二活性子层的活性材料包括功率型的活性材料。比如，第一活性子层的活性材料为能量型石墨，第二活性子层的活性材料为快充石墨。Optionally, the active material of the first active sublayer and the active material of the second active sublayer may be the same or different. Optionally, the active material of the first active sublayer includes an energy-type active material, and the active material of the second active sublayer includes a power-type active material. For example, the active material of the first active sublayer is energy-type graphite, and the active material of the second active sublayer is fast-charging graphite.
在一些实施方式中，以占第二活性子层的活性材料的质量百分数计，噻蒽类化合物的质量百分数≤5％。噻蒽类化合物的质量百分数在该范围内可以较好地兼顾改善孔隙率和电池容量。当噻蒽类化合物的质量百分数过大时，可能会降低负极活性材料的用量，导致电池容量降低。可选地，以占第二活性子层的活性材料的质量百分数计，噻蒽类化合物的质量百分数≥1。比如，以占第二活性子层的活性材料的质量百分数计，噻蒽类化合物的质量百分数为1.5％、2％、2.5％、3％、3.5％、4％、4.5％或5％等。可以理解的是，以占第二活性子层的活性材料的质量百分数计，噻蒽类化合物的质量百分数还可以在1％～5％范围内进行其他合适的选择。In some embodiments, the mass percentage of the thianthrene compound is ≤5% based on the mass percentage of the active material in the second active sublayer. The mass percentage of the thianthrene compound within this range can better balance the improvement of porosity and battery capacity. When the mass percentage of the thianthrene compound is too large, the amount of negative electrode active material may be reduced, resulting in a decrease in battery capacity. Optionally, the mass percentage of the thianthrene compound is ≥1 based on the mass percentage of the active material in the second active sublayer. For example, the mass percentage of the thianthrene compound is 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% based on the mass percentage of the active material in the second active sublayer. It is understandable that the mass percentage of the thianthrene compound can also be selected in the range of 1% to 5% based on the mass percentage of the active material in the second active sublayer.
本申请还提供了一种上述负极极片的制备方法，包括如下步骤：在负极集流体的至少一个表面之上采用上述负极浆料形成所述负极活性层。The present application also provides a method for preparing the above-mentioned negative electrode sheet, comprising the following steps: forming the negative electrode active layer on at least one surface of the negative electrode current collector using the above-mentioned negative electrode slurry.
可选地，负极活性层分为层叠设置的第一活性子层和第二活性子层，在集流体的至少一个表面之上形成第一活性子层，在第一活性子层之上采用上述负极浆料形成第二活性子层。.Optionally, the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is formed on at least one surface of the current collector, and the second active sublayer is formed on the first active sublayer using the above negative electrode slurry.
可选地，在集流体的至少一个表面之上形成第一活性子层是通过浆料形成第一活性子层。 可选地，形成第一活性子层的浆料中不含有上述负极组合物。Optionally, forming the first active sublayer on at least one surface of the current collector is forming the first active sublayer by slurry. Optionally, the slurry for forming the first active sublayer does not contain the negative electrode composition.
本申请还提供了一种噻蒽类化合物在负极浆料或负极极片中作为造孔剂的应用。可选地，噻蒽类化合物包括噻蒽、2-乙酰基噻蒽、2,7-二乙酰基噻蒽、2,7-二溴噻蒽以及2,7-二异丁酰基噻蒽中的一种或几种。可选地，噻蒽类化合物在标准大气压下的熔点＞100℃。The present application also provides an application of a thianthrene compound as a pore former in a negative electrode slurry or a negative electrode sheet. Optionally, the thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene. Optionally, the melting point of the thianthrene compound at standard atmospheric pressure is greater than 100°C.
本申请还提供了一种二次电池，包括上述负极极片及电解液，负极极片的负极活性层与电解液接触。这种二次电池适用于各种使用电池的用电装置，例如手机、便携式设备、笔记本电脑、电瓶车、电动玩具、电动工具、电动汽车、船舶和航天器等，例如，航天器包括飞机、火箭、航天飞机和宇宙飞船等。The present application also provides a secondary battery, comprising the above-mentioned negative electrode plate and an electrolyte, wherein the negative electrode active layer of the negative electrode plate is in contact with the electrolyte. The secondary battery is suitable for various electrical devices using batteries, such as mobile phones, portable devices, laptop computers, battery cars, electric toys, electric tools, electric cars, ships and spacecraft, etc. For example, the spacecraft includes airplanes, rockets, space shuttles and spacecrafts, etc.
可以理解的是，噻蒽类化合物在电解液中具有较好的溶解性。It can be understood that thianthrene compounds have good solubility in electrolyte.
可选地，电解液的溶剂包括碳酸二甲酯和碳酸二乙酯中的一种或两种。Optionally, the solvent of the electrolyte includes one or both of dimethyl carbonate and diethyl carbonate.
本申请还提供了一种用电装置，包括上述二次电池。The present application also provides an electrical device, comprising the above-mentioned secondary battery.
以下适当参照附图对本申请的二次电池、电池模块、电池包和用电装置进行说明。The secondary battery, battery module, battery pack, and electric device of the present application are described below with reference to the accompanying drawings as appropriate.
通常情况下，二次电池包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使离子通过。Generally, a secondary battery includes a positive electrode sheet, a negative electrode sheet, an electrolyte and a separator. During the battery charging and discharging process, active ions are embedded and released back and forth between the positive electrode sheet and the negative electrode sheet. The electrolyte plays the role of conducting ions between the positive electrode sheet and the negative electrode sheet. The separator is set between the positive electrode sheet and the negative electrode sheet, mainly to prevent the positive and negative electrodes from short-circuiting, while allowing ions to pass through.
正极极片Positive electrode
正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，所述正极膜层包括正极活性材料。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, wherein the positive electrode film layer includes a positive electrode active material.
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极活性材料层设置在正极集流体相对的两个表面的其中任意一者或两者上。As an example, the positive electrode current collector has two surfaces facing each other in its thickness direction, and the positive electrode active material layer is disposed on any one or both of the two facing surfaces of the positive electrode current collector.
在一些实施方式中，所述正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。In some embodiments, the positive electrode current collector may be a metal foil or a composite current collector. For example, aluminum foil may 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 may 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 a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
作为示例，正极活性材料可包含本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活 性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO
2)、锂镍氧化物(如LiNiO
2)、锂锰氧化物(如LiMnO
2、LiMn
2O
4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi
1/3Co
1/3Mn
1/3O
2(也可以简称为NCM
333)、LiNi
0.5Co
0.2Mn
0.3O
2(也可以简称为NCM
523)、LiNi
0.5Co
0.25Mn
0.25O
2(也可以简称为NCM
211)、LiNi
0.6Co
0.2Mn
0.2O
2(也可以简称为NCM
622)、LiNi
0.8Co
0.1Mn
0.1O
2(也可以简称为NCM
811)、锂镍钴铝氧化物(如LiNi
0.85Co
0.15Al
0.05O
2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO
4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO
4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。所述正极活性材料在正极膜层中的重量比为80～100重量％，基于正极膜层的总重量计。
As an example, the positive electrode active material may include a positive electrode active material for a battery known in the art. As an example, the positive electrode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds. However, the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, examples of lithium transition metal oxides may include, but are not limited to , lithium cobalt oxide (such as LiCoO2 ), lithium nickel oxide (such as LiNiO2 ), lithium manganese oxide (such as LiMnO2 , LiMn2O4 ), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi1 / 3Co1 / 3Mn1 / 3O2 (also referred to as NCM333 ), LiNi0.5Co0.2Mn0.3O2 (also referred to as NCM523 ) , LiNi0.5Co0.25Mn0.25O2 (also referred to as NCM211 ) , LiNi0.6Co0.2Mn0.2O2 (also referred to as NCM622 ), LiNi0.8Co0.1Mn0.1O2 (also referred to as NCM811 ), lithium nickel cobalt aluminum oxide ( such as LiNi 0.85 Co 0.15 Al 0.05 O 2 ) and at least one of its modified compounds. Examples of lithium-containing phosphates with an olivine structure may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon. The weight ratio of the positive electrode active material in the positive electrode film layer is 80 to 100 weight %, based on the total weight of the positive electrode film layer.
在一些实施方式中，正极膜层还可选地包括粘结剂。作为示例，所述粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。所述粘结剂在正极膜层中的重量比为0～20重量％，基于正极膜层的总重量计。In some embodiments, the positive electrode film layer may also optionally include 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 fluorine-containing acrylate resin. The weight ratio of the binder in the positive electrode film layer is 0 to 20% by weight, based on the total weight of the positive electrode film layer.
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，所述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。所述导电剂在正极膜层中的重量比为0～20重量％，基于正极膜层的总重量计。In some embodiments, the positive electrode film layer may further include 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. The weight ratio of the conductive agent in the positive electrode film layer is 0 to 20 weight %, based on the total weight of the positive electrode film layer.
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料，其中所述正极浆料固含量为40～80wt％，室温下的粘度调整到5000～25000mPa·s，将正极浆料涂覆在正极集流体的表面，烘干后经过冷轧机冷压后形成正极极片；正极粉末涂布单位面密度为150-350mg/m
2，正极极片压实密度为3.0-3.6g/cm
3，可选为3.3-3.5g/cm
3。所述压实密度的计算公式为：压实密度＝涂布面密度/(挤压后极片厚度-集流体厚度)。
In some embodiments, the positive electrode sheet can be prepared by the following method: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry, wherein the positive electrode slurry has a solid content of 40 to 80 wt%, and the viscosity at room temperature is adjusted to 5000 to 25000 mPa·s, the positive electrode slurry is coated on the surface of the positive current collector, and after drying, the positive electrode sheet is formed after cold pressing by a cold rolling mill; the positive electrode powder coating unit area density is 150-350 mg/m 2 , and the positive electrode sheet compaction density is 3.0-3.6 g/cm 3 , and can be optionally 3.3-3.5 g/cm 3 . The compaction density is calculated as follows: compaction density = coating area density/(thickness of the sheet after extrusion-thickness of the current collector).
可理解的是，本申请实施例中正极极片可以是将上述正极极片作为正极极片主体，并在该正极极片主体的表面形成固体电解质界面膜而制成。It is understandable that the positive electrode sheet in the embodiment of the present application can be made by using the above-mentioned positive electrode sheet as the positive electrode sheet body and forming a solid electrolyte interface film on the surface of the positive electrode sheet body.
负极极片Negative electrode
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，所述负极 膜层包括负极活性材料。The negative electrode sheet includes a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer includes a negative electrode active material.
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。As an example, the negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
在一些实施方式中，所述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。In some embodiments, the negative electrode current collector may be a metal foil or a composite current collector. For example, as the metal foil, copper 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 substrate. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。所述锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。所述负极活性材料在负极膜层中的重量比为70～100重量％，基于负极膜层的总重量计。In some embodiments, the negative electrode active material may adopt the negative electrode active material for the battery known in the art. As an example, the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material and lithium titanate. The silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys. However, the present application is not limited to these materials, and other traditional materials that can be used as negative electrode active materials for batteries can also be used. These negative electrode active materials can be used alone or in combination of two or more. The weight ratio of the negative electrode active material in the negative electrode film layer is 70 to 100 weight%, based on the total weight of the negative electrode film layer.
在一些实施方式中，负极膜层还可选地包括粘结剂。所述粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。所述粘结剂在负极膜层中的重量比为0～30重量％，基于负极膜层的总重量计。In some embodiments, the negative electrode film layer may further include a binder. The binder may be selected from at least one of 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). The weight ratio of the binder in the negative electrode film layer is 0 to 30% by weight, based on the total weight of the negative electrode film layer.
在一些实施方式中，负极膜层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。所述导电剂在负极膜层中的重量比为0～20重量％，基于负极膜层的总重量计。In some embodiments, the negative electrode film layer may further include 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. The weight ratio of the conductive agent in the negative electrode film layer is 0 to 20 weight %, based on the total weight of the negative electrode film layer.
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。所述其他助剂在负极膜层中的重量比为0～15重量％，基于负极膜层的总重量计。In some embodiments, the negative electrode film layer may further include other additives, such as a thickener (such as sodium carboxymethyl cellulose (CMC-Na)), etc. The weight ratio of the other additives in the negative electrode film layer is 0 to 15 weight %, based on the total weight of the negative electrode film layer.
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料，其中所述负极浆料固含量为30～70wt％，室温下的粘度调整到2000～10000mPa·s；将所得到的负极浆料涂覆在负极集流体上，经过干燥工序，冷压例如对辊，得到负极极片。 负极粉末涂布单位面密度为75～220mg/m
2，负极极片压实密度1.2～2.0g/m
3。
In some embodiments, the negative electrode sheet can be prepared by the following method: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as deionized water) to form a negative electrode slurry, wherein the solid content of the negative electrode slurry is 30-70wt%, and the viscosity at room temperature is adjusted to 2000-10000mPa·s; the obtained negative electrode slurry is coated on the negative electrode collector, and after a drying process, cold pressing such as rolling, a negative electrode sheet is obtained. The negative electrode powder coating unit area density is 75-220mg/ m2 , and the negative electrode sheet compaction density is 1.2-2.0g/ m3 .
可以理解的是，本申请实施例中负极极片可以是将上述负极极片作为负极极片主体，并在该负极极片主体的表面形成固体电解质界面膜而制成。It can be understood that the negative electrode sheet in the embodiment of the present application can be made by using the above-mentioned negative electrode sheet as the negative electrode sheet body and forming a solid electrolyte interface film on the surface of the negative electrode sheet body.
电解质Electrolytes
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。The electrolyte plays the role of conducting ions between the positive electrode and the negative electrode. The present application has no specific restrictions on the type of electrolyte, which can be selected according to needs. For example, the electrolyte can be liquid, gel or all-solid.
在一些实施方式中，所述电解质采用电解液。所述电解液包括电解质盐和溶剂。In some embodiments, the electrolyte is an electrolyte solution, which includes an electrolyte salt and a solvent.
在一些实施方式中，电解质盐可选自六氟磷酸锂(LiPF
6)、四氟硼酸锂(LiBF
4)、高氯酸锂(LiClO
4)、六氟砷酸锂(LiAsF
6)、双氟磺酰亚胺锂(LiFSI)、双三氟甲磺酰亚胺锂(LiTFSI)、三氟甲磺酸锂(LiTFS)、二氟草酸硼酸锂(LiDFOB)、二草酸硼酸锂(LiBOB)、二氟磷酸锂(LiPO
2F
2)、二氟二草酸磷酸锂(LiDFOP)及四氟草酸磷酸锂(LiTFOP)中的一种或几种。所述电解质盐的浓度通常为0.5～5mol/L。
In some embodiments, the electrolyte salt may be selected from one or more of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluorooxalatoborate (LiDFOB), lithium dioxalatoborate (LiBOB), lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorobis(oxalatophosphate) (LiDFOP) and lithium tetrafluorooxalatophosphate (LiTFOP). The concentration of the electrolyte salt is generally 0.5 to 5 mol/L.
在一些实施方式中，溶剂可选自氟代碳酸乙烯酯(FEC)、碳酸亚乙酯(EC)、碳酸亚丙基酯(PC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸亚丁酯(BC)、甲酸甲酯(MF)、乙酸甲酯(MA)、乙酸乙酯(EA)、乙酸丙酯(PA)、丙酸甲酯(MP)、丙酸乙酯(EP)、丙酸丙酯(PP)、丁酸甲酯(MB)、丁酸乙酯(EB)、1,4-丁内酯(GBL)、环丁砜(SF)、二甲砜(MSM)、甲乙砜(EMS)及二乙砜(ESE)中的一种或几种。In some embodiments, the solvent can be selected from one or more of fluoroethylene carbonate (FEC), ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), butylene carbonate (BC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), ethyl methyl sulfone (EMS) and diethyl sulfone (ESE).
在一些实施方式中，所述电解液还可选地包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。In some embodiments, the electrolyte may further include additives, such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
隔离膜Isolation film
在一些实施方式中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。In some embodiments, the secondary battery further includes a separator. The present application has no particular limitation on the type of separator, and any known porous separator with good chemical stability and mechanical stability can be selected.
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。In some embodiments, the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The isolation membrane can be a single-layer film or a multi-layer composite film, without particular limitation. When the isolation membrane is a multi-layer composite film, the materials of each layer can be the same or different, without particular limitation.
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。In some embodiments, the positive electrode sheet, the negative electrode sheet, and the separator may be formed into an electrode assembly by a winding process or a lamination process.
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。In some embodiments, the secondary battery may include an outer package, which may be used to encapsulate the electrode assembly and the electrolyte.
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图1是作为一个示例的方形结构的二次电池5。In some embodiments, the outer packaging of the secondary battery can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc. The outer packaging of the secondary battery can also be a soft package, such as a bag-type soft package. The material of the soft package can be plastic, and as plastic, polypropylene, polybutylene terephthalate, and polybutylene succinate can be listed. The present application has no particular restrictions on the shape of the secondary battery, which can be cylindrical, square, or other arbitrary shapes. For example, FIG. 1 is a secondary battery 5 of a square structure as an example.
在一些实施方式中，参照图2，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。In some embodiments, referring to FIG. 2 , the outer package may include a shell 51 and a cover plate 53. Among them, the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity. The shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity. The positive electrode sheet, the negative electrode sheet and the isolation film can form an electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is encapsulated in the receiving cavity. The electrolyte is infiltrated in the electrode assembly 52. The number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
在一些实施方式中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。In some embodiments, secondary batteries may be assembled into a battery module. The number of 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.
图3是作为一个示例的电池模块4。参照图3，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。FIG3 is a battery module 4 as an example. Referring to FIG3 , in the battery module 4, a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, they may also be arranged in any other manner. Further, the plurality of secondary batteries 5 may be fixed by fasteners.
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。Optionally, the battery module 4 may further include a housing having a housing space, and the plurality of secondary batteries 5 are housed in the housing space.
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。In some embodiments, the battery modules described above may also be assembled into a battery pack. The battery pack may contain one or more battery modules, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
图4和图5是作为一个示例的电池包1。参照图4和图5，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。FIG4 and FIG5 are battery packs 1 as an example. Referring to FIG4 and FIG5, the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 to form a closed space for accommodating the battery modules 4. The plurality of battery modules 4 can be arranged in the battery box in any manner.
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手 机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能***等，但不限于此。In addition, the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application. The secondary battery, battery module, or battery pack can be used as a power source for the electrical device, and can also be used as an energy storage unit for the electrical device. The electrical device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。As the electrical device, a secondary battery, a battery module or a battery pack may be selected according to its usage requirements.
图6是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。Fig. 6 is an example of an electric device. The electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc. In order to meet the electric device's requirements for high power and high energy density of secondary batteries, a battery pack or a battery module may be used.
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。Another example of a device may be a mobile phone, a tablet computer, a notebook computer, etc. Such a device is usually required to be thin and light, and a secondary battery may be used as a power source.
实施例Example
为了使本申请所解决的技术问题、技术方案及有益效果更加清楚，以下将结合实施例和附图对本申请进行进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本申请及其应用的任何限制。基于本申请中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例都属于本申请保护的范围。In order to make the technical problems, technical solutions and beneficial effects solved by the present application clearer, the present application will be further described in detail below in conjunction with the embodiments and drawings. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present application and its applications. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without creative work belong to the scope of protection of the present application.
实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.
实施例1Example 1
(1)制备负极浆料(1) Preparation of negative electrode slurry
按重量份计，取石墨100份，去离子水130份，炭黑2份，羧甲基纤维素(CMC)2份，丁苯橡胶(SBR)4份，噻嗯类化合物3份，噻蒽类化合物的CAS号：92-85-3，噻蒽类化合物的D50为2μm。In parts by weight, take 100 parts of graphite, 130 parts of deionized water, 2 parts of carbon black, 2 parts of carboxymethyl cellulose (CMC), 4 parts of styrene-butadiene rubber (SBR), 3 parts of thianthrene compounds, the CAS number of thianthrene compounds is: 92-85-3, and the D50 of thianthrene compounds is 2 μm.
先将CMC与去离子水在真空度小于-0.08MPa的条件下搅拌3小时得到CMC水溶液，然后将炭黑、SBR、石墨、噻嗯类化合物加入CMC水溶液中，在真空度小于-0.08MPa的条件下充分搅拌7小时，得到负极浆料。First, CMC and deionized water were stirred for 3 hours under the condition of vacuum degree less than -0.08MPa to obtain CMC aqueous solution, and then carbon black, SBR, graphite, and thionyl compounds were added to the CMC aqueous solution, and fully stirred for 7 hours under the condition of vacuum degree less than -0.08MPa to obtain negative electrode slurry.
(2)制备负极极片(2) Preparation of negative electrode sheet
将(1)中得到的负极浆料均匀地涂布在厚度为12μm的铜箔表面，再在95℃烘干水分，得到负极极片预成品。然后对负极极片预成品进行压延，压延速度为15m/min，再对压延后的极片进行热处理，热处理条件的真空度小于-0.08MPa，温度为140℃，烘烤时间为15min， 得到厚度为120μm，压实密度为1.32g/cm
3的负极极片，最后切片，得到长×宽×厚＝491mm×43.5mm×120μm的负极极片。
The negative electrode slurry obtained in (1) is evenly coated on the surface of a copper foil with a thickness of 12 μm, and then dried at 95°C to obtain a negative electrode pre-finished product. The negative electrode pre-finished product is then rolled at a rolling speed of 15 m/min, and then the rolled electrode is heat-treated under the conditions of vacuum less than -0.08 MPa, temperature of 140°C, and baking time of 15 min to obtain a negative electrode electrode with a thickness of 120 μm and a compaction density of 1.32 g/cm 3 , and finally sliced to obtain a negative electrode electrode with a length×width×thickness=491 mm×43.5 mm×120 μm.
(3)制备正极极片(3) Preparation of positive electrode sheet
称取磷酸铁锂(LiFePO
4)1.5kg，以及导电炭黑(CB)、聚偏二氟乙烯(PVDF)、N-甲基吡咯烷酮(NMP)按照重量比LiFePO
4:CB:PVDF:NMP＝100:5:3.5:110配制正极浆料，搅拌均匀后涂在12μm厚的铝箔上，然后100℃干燥10分钟，然后用压片机压片，最后切片，得到长×宽×厚＝471mm×42mm×160μm的正极极片。
1.5 kg of lithium iron phosphate (LiFePO 4 ) was weighed, and conductive carbon black (CB), polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) were prepared according to the weight ratio of LiFePO 4 :CB:PVDF:NMP=100:5:3.5:110 to prepare a positive electrode slurry. After stirring evenly, the slurry was coated on a 12 μm thick aluminum foil, then dried at 100° C. for 10 minutes, and then pressed into sheets using a tablet press. Finally, the slurry was sliced to obtain a positive electrode sheet with a length×width×thickness=471 mm×42 mm×160 μm.
(4)制备锂离子电池(4) Preparation of lithium-ion batteries
将前述步骤(2)和(3)制得的负极极片、正极极片与厚度为25μm的聚丙烯膜隔膜按照正极极片、隔膜、负极极片的次序依次叠放，然后卷绕，制成锂离子电池的极芯。将该极芯放入高50mm、厚5mm、宽34mm的钢制方型锂离子电池外壳中，然后注入3.8g电解液，最后密封电池外壳，制成053450锂离子电池。其中，电解液是LiPF
6/EC+DEC+EMC+DMC体系。
The negative electrode sheet, positive electrode sheet and 25 μm thick polypropylene film separator prepared in the above steps (2) and (3) are stacked in the order of positive electrode sheet, separator and negative electrode sheet, and then wound to make the electrode core of the lithium ion battery. The electrode core is placed in a steel square lithium ion battery shell with a height of 50 mm, a thickness of 5 mm and a width of 34 mm, and then 3.8 g of electrolyte is injected, and finally the battery shell is sealed to make a 053450 lithium ion battery. The electrolyte is a LiPF 6 /EC+DEC+EMC+DMC system.
实施例2Example 2
与实施例1相比，本实施例的不同之处在于：负极浆料中，噻蒽类化合物的重量份为1份。Compared with Example 1, the difference of this example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 1 part.
实施例3Example 3
与实施例1相比，本实施例的不同之处在于：负极浆料中，噻蒽类化合物的重量份为2份。Compared with Example 1, the difference of this example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 2 parts.
实施例4Example 4
与实施例1相比，本实施例的不同之处在于：负极浆料中，噻蒽类化合物的重量份为4份。Compared with Example 1, the difference of this example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 4 parts.
实施例5Example 5
与实施例1相比，本实施例的不同之处在于：负极浆料中，噻蒽类化合物的重量份为5份。Compared with Example 1, the difference of this example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 5 parts.
实施例6Example 6
与实施例1相比，本实施例的不同之处在于：负极活性层分为层叠设置的第一活性子层和第二活性子层，第一活性子层位于负极集流体的至少一个表面之上，第二活性子层位于第一活性子层之上。第一活性子层的活性浆料与实施例1中步骤(1)的不同之处在于负极浆料 不含噻蒽类化合物，第二活性子层的活性浆料为实施例1中步骤(1)得到的负极浆料。Compared with Example 1, the difference of this embodiment is that the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is located on at least one surface of the negative electrode current collector, and the second active sublayer is located on the first active sublayer. The difference between the active slurry of the first active sublayer and step (1) in Example 1 is that the negative electrode slurry does not contain thianthrene compounds, and the active slurry of the second active sublayer is the negative electrode slurry obtained in step (1) in Example 1.
本实施例中负极极片的制备方法为：上述制备的第一活性层负极浆料均匀地涂布在厚度为12μm的铜箔表面，再将上述制备的第二活性层负极浆料均匀涂布在第一活性层负极之上，然后在95℃烘干水分，得到负极极片预成品。The preparation method of the negative electrode sheet in this embodiment is: the first active layer negative electrode slurry prepared above is evenly coated on the surface of a copper foil with a thickness of 12 μm, and then the second active layer negative electrode slurry prepared above is evenly coated on the first active layer negative electrode, and then the water is dried at 95°C to obtain a pre-finished negative electrode sheet.
实施例7Example 7
与实施例1相比，本实施例的不同之处在于，负极浆料中，噻蒽类化合物为2-乙酰基噻蒽。Compared with Example 1, the difference of this example is that in the negative electrode slurry, the thianthrene compound is 2-acetylthianthrene.
实施例8Example 8
与实施例1相比，本实施例的不同之处在于，负极浆料中，噻蒽类化合物为2,7-二乙酰基噻蒽。Compared with Example 1, the difference of this example is that in the negative electrode slurry, the thianthrene compound is 2,7-diacetylthianthrene.
实施例9Example 9
与实施例1相比，本实施例的不同之处在于，负极浆料中，噻蒽类化合物为2,7-二溴噻蒽。Compared with Example 1, the difference of this example is that in the negative electrode slurry, the thianthrene compound is 2,7-dibromothianthrene.
实施例10Example 10
与实施例1相比，本实施例的不同之处在于，负极浆料中，噻蒽类化合物为2,7-二异丁酰基噻蒽。Compared with Example 1, the difference of this example is that in the negative electrode slurry, the thianthrene compound is 2,7-diisobutyrylthianthrene.
对比例1Comparative Example 1
与实施例1相比，本对比例的不同之处在于：负极浆料中，噻蒽类化合物的重量份为0份。Compared with Example 1, the difference of this comparative example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 0 parts.
对比例2Comparative Example 2
与实施例1相比，本对比例的不同之处在于：负极浆料中，噻蒽类化合物的重量份为6份。Compared with Example 1, the difference of this comparative example is that in the negative electrode slurry, the weight portion of the thianthrene compound is 6 parts.
对比例3Comparative Example 3
与实施例1相比，本实施例的不同之处在于：负极浆料中，噻蒽类化合物的D50为0.2μm。Compared with Example 1, the difference of this example is that in the negative electrode slurry, the D50 of the thianthrene compound is 0.2 μm.
对比例4Comparative Example 4
与实施例1相比，本对比例的不同之处在于：负极浆料中，噻蒽类化合物的D50为10μm。Compared with Example 1, the difference of this comparative example is that in the negative electrode slurry, the D50 of the thianthrene compound is 10 μm.
对比例5Comparative Example 5
与实施例6相比，本对比例的不同之处在于：第一活性子层的活性浆料加入噻蒽类造孔剂，第二活性子层为不含造孔剂的负极浆料。Compared with Example 6, the difference of this comparative example is that a thianthrene pore former is added to the active slurry of the first active sublayer, and the second active sublayer is a negative electrode slurry without a pore former.
测试例Test Case
对实施例和对比例中负极活性层的孔隙率、锂离子电池的容量、锂离子电池的循环性能、锂离子电池的倍率性能、电池的内阻进行测试，测试结果如表1所示。The porosity of the negative electrode active layer, the capacity of the lithium ion battery, the cycle performance of the lithium ion battery, the rate performance of the lithium ion battery, and the internal resistance of the battery in the embodiments and comparative examples were tested, and the test results are shown in Table 1.
其中，负极活性层的孔隙率的测试方法为：气体置换法，样品孔体积占总面积的百分比，Porosity＝(V1-V2)/V1*100％，V1：样品的表观体积，V2：样品的真实体积。The porosity of the negative electrode active layer is tested by gas replacement method, the pore volume of the sample is the percentage of the total area, Porosity = (V1-V2)/V1*100%, V1: the apparent volume of the sample, V2: the actual volume of the sample.
锂离子电池的容量的测试方法为：在25℃下，先以1C的恒定电流对电池充电至3.65V，进一步以3.65V恒定电压充电至电流为0.05C，然后以1C的恒定电流将电池放电至2.5V，此为一个充放电循环过程，此次的放电容量为第1次循环的放电容量。The test method for the capacity of a lithium-ion battery is as follows: at 25°C, first charge the battery to 3.65V at a constant current of 1C, then charge it to a current of 0.05C at a constant voltage of 3.65V, and then discharge it to 2.5V at a constant current of 1C. This is a charge and discharge cycle process, and the discharge capacity this time is the discharge capacity of the first cycle.
锂离子电池的倍率性能的测试方法为：在25℃下，先以1C的恒定电流对电池充电至3.65V，进一步以3.65V恒定电压充电至电流为0.05C，然后以1C的恒定电流将电池放电至2.5V，此为一个充放电循环过程，此次的放电容量为第1次循环的放电容量；再以1C的恒定电流对电池单体充电至3.65V，进一步以3.65V恒定电压充电至电流为0.05C，然后以2C的恒定电流将电池放电至2.5V，此为一个充放电循环过程，此次的放电容量为第2次循环的放电容量，第2次循环放电容量与第1次循环放电容量比值记为2C倍率容量保持率。The test method for the rate performance of lithium-ion batteries is as follows: at 25°C, the battery is first charged to 3.65V at a constant current of 1C, further charged to a current of 0.05C at a constant voltage of 3.65V, and then discharged to 2.5V at a constant current of 1C. This is a charge and discharge cycle process, and the discharge capacity this time is the discharge capacity of the first cycle; then the battery cell is charged to 3.65V at a constant current of 1C, further charged to a current of 0.05C at a constant voltage of 3.65V, and then discharged to 2.5V at a constant current of 2C. This is a charge and discharge cycle process, and the discharge capacity this time is the discharge capacity of the second cycle, and the ratio of the discharge capacity of the second cycle to the discharge capacity of the first cycle is recorded as the 2C rate capacity retention rate.
电池的内阻测试方法为：采用1KHz的正弦波电流，来测试引起的压降，计算内阻。The internal resistance test method of the battery is: use a 1KHz sinusoidal current to test the voltage drop caused and calculate the internal resistance.
表1Table 1
由表1可以看出，实施例1～实施例10中负极极片的孔隙率适中，可以使电解液对负极极片更好地浸润，同时电池的容量和倍率性能较高，内阻较低。It can be seen from Table 1 that the porosity of the negative electrode plates in Examples 1 to 10 is moderate, which allows the electrolyte to better infiltrate the negative electrode plates. At the same time, the battery has high capacity and rate performance and low internal resistance.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.
Claims (17)
- 一种负极组合物，其特征在于，包括负极活性材料和噻蒽类化合物。A negative electrode composition, characterized by comprising a negative electrode active material and a thianthrene compound.
- 根据权利要求1所述的负极组合物，其特征在于，所述噻蒽类化合物具有如式(Ⅰ)所示的结构：The negative electrode composition according to claim 1, characterized in that the thianthrene compound has a structure as shown in formula (I):
其中，R 1和R 2分别独立地选自H、D、F、Cl、Br、I、碳原子数为1～10的烷基、碳原子数为1～10的酰基。 wherein R1 and R2 are independently selected from H, D, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms. - 根据权利要求1或2所述的负极组合物，其特征在于，所述噻蒽类化合物满足以下特征中的一种或多种：The negative electrode composition according to claim 1 or 2, characterized in that the thianthrene compound satisfies one or more of the following characteristics:(1)所述噻蒽类化合物包括噻蒽、2-乙酰基噻蒽、2,7-二乙酰基噻蒽、2,7-二溴噻蒽以及2,7-二异丁酰基噻蒽中的一种或多种；(1) The thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene;(2)所述噻蒽类化合物在标准大气压下的熔点＞100℃；(2) The melting point of the thianthrene compound at standard atmospheric pressure is greater than 100° C.;(3)以占所述负极活性材料的质量百分数计，所述噻蒽类化合物的质量百分数≤5％；(3) The mass percentage of the thianthrene compound is ≤5% based on the mass percentage of the negative electrode active material;可选地，以占所述负极活性材料的质量百分数计，所述噻蒽类化合物的质量百分数为1％～5％；Optionally, the mass percentage of the thianthrene compound is 1% to 5% based on the mass percentage of the negative electrode active material;(4)所述噻蒽类化合物的D50为0.5μm～5μm。(4) The D50 of the thianthrene compound is 0.5 μm to 5 μm.
- 权利要求1～3中任一项所述的负极组合物的制备方法，其特征在于，包括如下步骤：The method for preparing the negative electrode composition according to any one of claims 1 to 3, characterized in that it comprises the following steps:将所述负极活性材料和所述噻蒽类化合物混合。The negative electrode active material and the thianthrene compound are mixed.
- 一种负极浆料，其特征在于，包括溶剂和权利要求1～3中任一项所述的负极组合物。A negative electrode slurry, characterized by comprising a solvent and the negative electrode composition according to any one of claims 1 to 3.
- 权利要求5所述的负极浆料的制备方法，其特征在于，包括如下步骤：The method for preparing the negative electrode slurry according to claim 5, characterized in that it comprises the following steps:将所述溶剂和所述负极组合物混合。The solvent and the negative electrode composition are mixed.
- 一种负极极片，其特征在于，包括：A negative electrode plate, characterized by comprising:负极集流体；及Anode current collector; and负极活性层，所述负极活性层设于所述负极集流体的至少一个表面之上，所述负极活性层包括权利要求1～3中任一项所述的负极组合物。A negative electrode active layer is provided on at least one surface of the negative electrode current collector, and the negative electrode active layer comprises the negative electrode composition according to any one of claims 1 to 3.
- 根据权利要求7所述的负极极片，其特征在于，所述负极活性层分为层叠设置的第一活性子层和第二活性子层，所述第一活性子层位于所述负极集流体的至少一个表面之上，所述第二活性子层位于所述第一活性子层之上；所述负极组合物位于所述第二活性子层。The negative electrode plate according to claim 7 is characterized in that the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is located on at least one surface of the negative electrode collector, and the second active sublayer is located on the first active sublayer; the negative electrode composition is located in the second active sublayer.
- 根据权利要求8所述的负极极片，其特征在于，以占所述第二活性子层的活性材料的质量百分数计，所述噻蒽类化合物的质量百分数≤5％；The negative electrode sheet according to claim 8, characterized in that the mass percentage of the thianthrene compound is ≤5% based on the mass percentage of the active material in the second active sublayer;可选地，以占所述第二活性子层的活性材料的质量百分数计，所述噻蒽类化合物的质量百分数为1％～5％。Optionally, the mass percentage of the thianthrene compound is 1% to 5% based on the mass percentage of the active material of the second active sub-layer.
- 权利要求7～9中任一项所述的负极极片的制备方法，其特征在于，包括如下步骤：The method for preparing a negative electrode sheet according to any one of claims 7 to 9 is characterized in that it comprises the following steps:在所述负极集流体的至少一个表面之上采用权利要求5所述的负极浆料形成所述负极活性层。The negative electrode active layer is formed on at least one surface of the negative electrode current collector using the negative electrode slurry according to claim 5.
- 根据权利要求10所述的负极极片的制备方法，其特征在于，所述负极活性层分为层叠设置的第一活性子层和第二活性子层，在所述集流体的至少一个表面之上形成所述第一活性子层，在所述第一活性子层之上采用所述负极浆料形成所述第二活性子层。The method for preparing a negative electrode sheet according to claim 10 is characterized in that the negative electrode active layer is divided into a first active sublayer and a second active sublayer which are stacked, the first active sublayer is formed on at least one surface of the current collector, and the second active sublayer is formed on the first active sublayer using the negative electrode slurry.
- 噻蒽类化合物在负极浆料或负极极片中作为造孔剂的应用。Application of thianthrene compounds as pore formers in negative electrode slurry or negative electrode sheets.
- 根据权利要求12所述的应用，其特征在于，所述噻蒽类化合物具有如式(Ⅰ)所示的结构：The use according to claim 12, characterized in that the thianthrene compound has a structure as shown in formula (I):
其中，R 1和R 2分别独立地选自H、D、F、Cl、Br、I、碳原子数为1～10的烷基、碳原子数为1～10的酰基。 wherein R1 and R2 are independently selected from H, D, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms. - 根据权利要求12或13所述的应用，其特征在于，所述噻蒽类化合物满足以下特征中的一种或几种：The use according to claim 12 or 13, characterized in that the thianthrene compound satisfies one or more of the following characteristics:(1)所述噻蒽类化合物包括噻蒽、2-乙酰基噻蒽、2,7-二乙酰基噻蒽、2,7-二溴噻蒽以及2,7-二异丁酰基噻蒽中的一种或几种；(1) The thianthrene compound includes one or more of thianthrene, 2-acetylthianthrene, 2,7-diacetylthianthrene, 2,7-dibromothianthrene and 2,7-diisobutyrylthianthrene;(2)所述噻蒽类化合物在标准大气压下的熔点＞100℃。(2) The melting point of the thianthrene compound at standard atmospheric pressure is greater than 100°C.
- 一种二次电池，其特征在于，包括权利要求7～9中任一项所述的负极极 片；及A secondary battery, characterized by comprising the negative electrode sheet according to any one of claims 7 to 9; and电解液，所述负极极片的负极活性层与所述电解液接触。An electrolyte, wherein the negative electrode active layer of the negative electrode plate is in contact with the electrolyte.
- 根据权利要求15所述的二次电池，其特征在于，所述电解液的溶剂包括碳酸二甲酯和碳酸二乙酯中的一种或两种。The secondary battery according to claim 15, characterized in that the solvent of the electrolyte includes one or both of dimethyl carbonate and diethyl carbonate.
- 一种用电装置，其特征在于，包括权利要求15或16所述的二次电池。An electrical device, characterized by comprising the secondary battery according to claim 15 or 16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2022/121750 WO2024065181A1 (en) | 2022-09-27 | 2022-09-27 | Negative electrode composition and preparation method therefor, negative electrode slurry and preparation method therefor, negative electrode sheet and preparation method therefor, secondary battery, electric device, and use of thianthrene compound |
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| PCT/CN2022/121750 WO2024065181A1 (en) | 2022-09-27 | 2022-09-27 | Negative electrode composition and preparation method therefor, negative electrode slurry and preparation method therefor, negative electrode sheet and preparation method therefor, secondary battery, electric device, and use of thianthrene compound |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150333331A1 (en) * | 2014-05-13 | 2015-11-19 | Arizona Board Of Regents On Behalf Of Arizona State University | Electrochemical energy storage devices comprising self-compensating polymers |
| CN109312023A (en) * | 2016-08-05 | 2019-02-05 | 赢创德固赛有限公司 | Contain purposes of the polymer as charge storage of thianthrene |
| KR102013530B1 (en) * | 2018-10-23 | 2019-08-23 | 재단법인 하이브리드 인터페이스기반 미래소재 연구단 | Dye-Graphite anode material for Lithium Ion Battery and Manufacturing Mehtod Thereof |
| CN112467193A (en) * | 2021-01-28 | 2021-03-09 | 上海瑞浦青创新能源有限公司 | Safety lithium ion battery and preparation method thereof |
| CN114883677A (en) * | 2022-05-26 | 2022-08-09 | 上海瑞浦青创新能源有限公司 | Lithium pre-preparing method for lithium ion battery |
-
2022
- 2022-09-27 WO PCT/CN2022/121750 patent/WO2024065181A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150333331A1 (en) * | 2014-05-13 | 2015-11-19 | Arizona Board Of Regents On Behalf Of Arizona State University | Electrochemical energy storage devices comprising self-compensating polymers |
| CN109312023A (en) * | 2016-08-05 | 2019-02-05 | 赢创德固赛有限公司 | Contain purposes of the polymer as charge storage of thianthrene |
| KR102013530B1 (en) * | 2018-10-23 | 2019-08-23 | 재단법인 하이브리드 인터페이스기반 미래소재 연구단 | Dye-Graphite anode material for Lithium Ion Battery and Manufacturing Mehtod Thereof |
| CN112467193A (en) * | 2021-01-28 | 2021-03-09 | 上海瑞浦青创新能源有限公司 | Safety lithium ion battery and preparation method thereof |
| CN114883677A (en) * | 2022-05-26 | 2022-08-09 | 上海瑞浦青创新能源有限公司 | Lithium pre-preparing method for lithium ion battery |
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