WO2023130215A1 - 混合串联电池模组、电池包以及用电装置 - Google Patents

混合串联电池模组、电池包以及用电装置 Download PDF

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WO2023130215A1
WO2023130215A1 PCT/CN2022/070126 CN2022070126W WO2023130215A1 WO 2023130215 A1 WO2023130215 A1 WO 2023130215A1 CN 2022070126 W CN2022070126 W CN 2022070126W WO 2023130215 A1 WO2023130215 A1 WO 2023130215A1
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type
equal
cell
negative electrode
range
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English (en)
French (fr)
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刘倩
李全国
叶永煌
金海族
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP22888603.2A priority Critical patent/EP4246657A4/en
Priority to PCT/CN2022/070126 priority patent/WO2023130215A1/zh
Priority to CN202280039862.8A priority patent/CN117461186A/zh
Priority to US18/327,674 priority patent/US11799136B2/en
Publication of WO2023130215A1 publication Critical patent/WO2023130215A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4207—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells for several batteries or cells simultaneously or sequentially
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/267—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders having means for adapting to batteries or cells of different types or different sizes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This application relates to the technical field of secondary batteries, and more specifically, this application relates to a hybrid series battery module, a battery pack, and an electrical device.
  • Lithium-ion batteries are widely used in energy storage power systems such as water power, thermal power, wind power and solar power plants, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields. Due to the great development of lithium-ion batteries, higher requirements have been put forward for the improvement of their energy density, cycle performance and safety performance. However, in recent years, there has been a bottleneck period in the technological development of lithium-ion batteries. At the same time, due to the increase in the price of lithium resources, the cost of lithium-ion batteries has increased.
  • the present application was made in view of the above-mentioned problems, and an object thereof is to provide an improved battery module, a battery pack and an electric device including the improved battery module. Specifically, the present application properly mixes and arranges the first type of batteries such as sodium-ion batteries or potassium-ion batteries and the second type of batteries such as lithium-ion batteries, so that the first type of batteries and the second type of batteries
  • the second type of batteries can complement each other in terms of performance, thereby improving the overall performance of the battery module, including but not limited to energy density, low temperature performance, structural stability, safety, heat dissipation performance, industrial manufacturability, etc., while reducing The overall cost of the battery module.
  • the first aspect of the present application provides a hybrid series battery module, the hybrid series battery module includes: one or more first-type cells, each of the first-type cells includes a first negative electrode sheet; and one or more cells of the second type, each cell of the second type comprising a second negative electrode sheet.
  • the energy density of the first type of cells is lower than the energy density of the second type of cells.
  • the layer spacing d1 of the negative active material of the first negative electrode sheet is greater than the layer spacing d2 of the negative active material of the second negative electrode sheet.
  • the ratio d1/d2 of the interlayer distance d1 to the interlayer distance d2 is within a range of greater than or equal to 1.005 and less than or equal to 1.600.
  • the ratio d1/d2 of the interlayer distance d1 to the interlayer distance d2 is within a range of greater than or equal to 1.010 and less than or equal to 1.200. Further optionally, in a state of 0% charge, the ratio d1/d2 of the interlayer distance d1 to the interlayer distance d2 is within a range of greater than or equal to 1.100 and less than or equal to 1.170.
  • the energy density of the first type of cell matches the energy density of the second type of cell so that the volume V1 of the first type of cell is the same as that of the second type of cell
  • the ratio V1/V2 of the volume V2 is in the range of greater than 0.20 and less than or equal to 20.00.
  • the energy density of the first type of cell matches the energy density of the second type of cell so that the volume V1 of the first type of cell is equal to the volume V2 of the second type of cell
  • the ratio V1/V2 is in the range of 0.40 or more and 5.00 or less.
  • the energy density of the first type of cell matches the energy density of the second type of cell so that the volume V1 of the first type of cell is the same as the volume V2 of the second type of cell
  • the ratio V1/V2 is in the range of greater than or equal to 1.00 and less than or equal to 2.10.
  • the energy density of the first type of cell matches the energy density of the second type of cell so that the thickness T1 of the first type of cell is the same as that of the second type of cell
  • the ratio T1/T2 of the thickness T2 is in the range of greater than 1.00 and less than or equal to 20.00.
  • the energy density of the first type of cell matches the energy density of the second type of cell so that the thickness T1 of the first type of cell is equal to the thickness T2 of the second type of cell
  • the ratio T1/T2 is in the range of 1.02 or more and 5.00 or less.
  • the energy density of the first type of cell matches the energy density of the second type of cell so that the thickness T1 of the first type of cell is the same as the thickness T2 of the second type of cell
  • the ratio T1/T2 is in the range of greater than or equal to 1.05 and less than or equal to 2.10.
  • the ratio E1/E2 of the volumetric energy density E1 of the first type of cell to the volumetric energy density E2 of the second type of cell is in the range of greater than or equal to 0.20 and less than or equal to 1.00.
  • the ratio E1/E2 of the volumetric energy density E1 of the first type of cell to the volumetric energy density E2 of the second type of cell is within a range of greater than or equal to 0.25 and less than or equal to 0.90.
  • the ratio E1/E2 of the volumetric energy density E1 of the first type of cell to the volumetric energy density E2 of the second type of cell is within a range of greater than or equal to 0.30 and less than or equal to 0.86.
  • the ratio G1/G2 of the gravimetric energy density G1 of the first type of cell to the gravimetric energy density G2 of the second type of cell is in the range of greater than or equal to 0.20 and less than or equal to 1.00.
  • the ratio G1/G2 of the gravimetric energy density G1 of the first type of cell to the gravimetric energy density G2 of the second type of cell is within a range of greater than or equal to 0.30 and less than or equal to 0.99.
  • the ratio G1/G2 of the gravimetric energy density G1 of the first type of cell to the gravimetric energy density G2 of the second type of cell is in the range of greater than or equal to 0.40 and less than or equal to 0.95.
  • the ratio P1/P2 of the porosity P1 of the first negative electrode sheet to the porosity P2 of the second negative electrode sheet is greater than or equal to 0.75 and Less than or equal to the range of 3.00.
  • the ratio P1/P2 of the porosity P1 of the first negative electrode sheet to the porosity P2 of the second negative electrode sheet is greater than or equal to 0.80 and less than or equal to 2.00 within range.
  • the ratio P1/P2 of the porosity P1 of the first negative electrode sheet to the porosity P2 of the second negative electrode sheet is greater than or equal to 0.90 and less than or equal to 1.50 In the range.
  • the ratio S1/S2 of the average particle size S1 of the negative active material of the first negative electrode sheet to the average particle size S2 of the negative active material of the second negative electrode sheet is greater than or equal to 0.10 and less than 1.00.
  • the ratio S1/S2 of the average particle size S1 of the negative electrode active material of the first negative electrode sheet to the average particle size S2 of the negative electrode active material of the second negative electrode sheet is greater than or equal to 0.15 and less than or equal to 0.95 In the range.
  • the ratio S1/S2 of the average particle size S1 of the negative electrode active material of the first negative electrode sheet to the average particle size S2 of the negative electrode active material of the second negative electrode sheet is greater than or equal to 0.30 and less than or equal to within the range of 0.90.
  • the ratio N/M of the number N of the first type of cells to the number M of the second type of cells is greater than or equal to 1.
  • the ratio N/M of the number N of the first type of cells to the number M of the second type of cells is within a range of greater than or equal to 1.5 and less than or equal to 200.
  • the ratio N/M of the number N of the first type of cells to the number M of the second type of cells is within a range of greater than or equal to 2 and less than or equal to 100.
  • the first type of cells and the second type of cells are arranged at intervals.
  • the first type of cells are arranged at both ends and in the middle of the hybrid series battery module.
  • the second aspect of the present application provides a battery pack.
  • the battery pack includes the hybrid series battery module according to the first aspect of the present application.
  • the third aspect of the present application provides an electrical device.
  • the electric device includes the hybrid series battery module according to the first aspect of the present application or the battery pack according to the second aspect of the present application.
  • Figure 1A shows an exemplary cell arrangement for low energy density.
  • Figure 1B shows an exemplary cell arrangement for high energy density.
  • Figure 1C shows an exemplary cell arrangement with high energy density, low stress, and high thermal insulation.
  • Figures 2A and 2B illustrate an exemplary hybrid series battery module arrangement according to an embodiment of the application.
  • FIG. 3A shows a perspective view of a lower case of an exemplary battery case for a battery pack according to an embodiment of the present application.
  • Figure 3B shows a top view of the upper case of the exemplary battery case of Figure 3A.
  • Figure 3C shows a schematic cross-sectional view taken along line AA in Figure 3B.
  • Figure 4A shows a perspective view of an exemplary battery pack according to an embodiment of the present application.
  • Figure 4B shows a top view of the exemplary battery pack of Figure 4A.
  • Figure 4C shows a schematic cross-sectional view taken along line BB in Figure 4B.
  • a “range” as disclosed herein is defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Additionally, 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 are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range "a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
  • steps (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c) , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b) and so on.
  • the "comprising” and “comprising” mentioned in this application means open or closed.
  • the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
  • the term "or” is inclusive.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist).
  • battery cell refers to a single battery that can be charged and discharged independently.
  • the present application has no limitation on the shape of the battery core, which may be cylindrical, square or any other shape.
  • the first type of cells such as sodium-ion cells, potassium-ion cells
  • the second type of cells such as lithium-ion cells
  • the radii of active ions for reversible deintercalation are different, and the deintercalation mechanism is also different.
  • the two types of cells are mixed and arranged, they restrict each other, and there are often contradictions.
  • the battery module obtained by the mixed arrangement On the contrary, the performance of the battery may decrease, and even make the battery module fail.
  • Those skilled in the art have always expected to transform the performance of the two different types of cells in the hybrid series battery module into complementary advantages, but before this application, no solution has been found to overcome the constraints between the two different types of cells. contradictory approach.
  • the active material with small layer spacing has high crystallinity (that is, the long-range order of the crystal structure) and strong anisotropy, resulting in a large rebound of the pole piece, and the expansion force of the cell increases rapidly during repeated charging and discharging.
  • the layer spacing of the negative active material in the negative electrode sheet of the battery cell is larger, the radius of the active ions allowed to intercalate between the layers is larger, and the active ions are easier to deintercalate from the interlayer structure, and thus the kinetics are better.
  • Active materials with large layer spacing have low crystallinity (that is, the long-range order of the crystal structure) and strong isotropy, resulting in less rebound of the pole piece, and slower increase in expansion force of the cell during repeated charge and discharge.
  • the layer distance d1 of the negative electrode active material of the first type of battery is greater than the layer distance d2 of the negative electrode active material of the second type of battery.
  • the degree of matching between the layer spacing of the negative electrode active material of the first type of battery and the second type of battery may have a great impact on the performance of the assembled battery module/battery pack.
  • This application uses the ratio d1/d2 between the layer spacing d1 of the negative electrode active material of the first type of battery and the layer spacing d2 of the negative electrode active material of the second type of battery to represent this matching degree, and uses this matching degree
  • the performance of the first type of battery cell and the second type of battery cell is successfully complemented, thereby improving the overall performance of the obtained battery module.
  • this application proposes a hybrid series battery module, which may include one or more first-type cells and one or more second-type cells, where each One first-type cell may include a first negative pole piece, and each second-type battery cell may include a second negative pole piece.
  • the energy density of the first type of cells may be lower than the energy density of the second type of cells.
  • the layer spacing d1 of the negative active material of the first negative electrode sheet may be greater than the layer spacing d2 of the negative active material of the second negative electrode sheet.
  • the ratio d1/d2 of the interlayer distance d1 to the interlayer distance d2 can be in the range of greater than or equal to 1.005 and less than or equal to 1.600 .
  • d1/d2 exceeds the above range, it may cause the active ions of the first type of cell to be unable to embed the negative active material, or the first type of cell and the second type of cell have fewer active ions embedded in the negative active material, As a result, the capacity of the battery module is low and the rate performance is poor. On the contrary, if d1/d2 is within the above range, the obtained battery module has relatively high capacity and good rate performance. At the same time, within the above range, d1 and d2 are relatively close, which is beneficial to improve the overall dynamic performance of the battery module and increase the expansion force of the battery cell during repeated charging and discharging. Especially for the increase of the cell expansion force of the battery module, it is very difficult to reduce the increase of the expansion force due to the difference in the chemical system of the two types of cells.
  • the ratio d1/d2 of the interlayer distance d1 to the interlayer distance d2 may be in the range of greater than or equal to 1.010 and less than or equal to 1.200. Additionally or alternatively, the ratio d1/d2 of the interlayer distance d1 to the interlayer distance d2 may be in a range of greater than or equal to 1.100 and less than or equal to 1.170 in a 0% state of charge.
  • the ratio d1/d2 may be, for example, 1.005, 1.010, 1.015, 1.020, 1.025, 1.030, 1.035, 1.040, 1.045, 1.050, 1.055, 1.060, 1.065, 1.070, 1.075, 1.080, 1.085, 1.090, 1.095, 1.100 , 1.105, 1.110, 1.115, 1.120, 1.125, 1.130, 1.135, 1.140, 1.145, 1.150, 1.155, 1.160, 1.165, 1.170, 1.175, 1.180, 1.185, 1.190, 1.195, 1.200, 1.205, 1.210, 1.215, 1.220, 1.225 , 1.230, 1.235, 1.240, 1.245, 1.250, 1.255, 1.260, 1.265, 1.270, 1.275, 1.280, 1.285, 1.290, 1.295, 1.300, 1.305, 1.310, 1.315, 1.320, 1.325, 1.330, 1.335, 1.340, 1.3
  • the first type of electric core can be a sodium ion battery chemical system, including but not limited to: Prussian blue derivatives/hard carbon system, polyanionic fast ion conductor sodium vanadium phosphate (or Sodium vanadium fluorophosphate, sodium vanadium oxyfluoride phosphate)/hard carbon system, transition metal oxide/hard carbon system, etc.; and the second type of cell can be a cell that uses an active material with an olivine structure as the main positive electrode material (such as LiFePO 4 , LiMn 0.6 Fe 0.4 PO 4 ), batteries using layered structure of nickel-cobalt lithium manganate as the main positive electrode material (such as LiNi 0.60 Co 0.10 Mn 0.30 O 2 ), etc.
  • This application can also significantly improve the dynamic performance of single cells and battery modules through the following further optimization design, effectively reduce the local stress inside the battery module, and improve the structural stability and stability of the battery module. security etc.
  • the energy density of the cell can be volume energy density or weight energy density.
  • the energy density of the first type of cell is lower than the energy density of the second type of cell.
  • the volumetric energy density E1 of the first type of battery cells may be in the range of, for example, 200 to 450 Wh/L.
  • the volumetric energy density E2 of the second type of battery cell may be in the range of, for example, 450 to 750 Wh/L.
  • the gravimetric energy density G1 of the first type of battery cells may be in the range of, for example, 100 to 220 Wh/Kg.
  • the gravimetric energy density G2 of the second type of battery cells may be in the range of, for example, 220 to 350 Wh/Kg.
  • the ratio E1/E2 of the volumetric energy density E1 of the first type of cell to the volumetric energy density E2 of the second type of cell can be greater than or equal to 0.20 and less than or equal to 1.00 within range. In an optional embodiment, the ratio E1/E2 of the volumetric energy density E1 of the first type of cell to the volumetric energy density E2 of the second type of cell may be within a range of greater than or equal to 0.25 and less than or equal to 0.90. In yet another optional embodiment, the ratio E1/E2 of the volumetric energy density E1 of the first type of cell to the volumetric energy density E2 of the second type of cell may be within a range of greater than or equal to 0.30 and less than or equal to 0.86.
  • the ratio E1/E2 may be, for example, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38 , 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63 , 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88 , 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97
  • the ratio G1/G2 of the gravimetric energy density G1 of the first type of cell to the gravimetric energy density G2 of the second type of cell can be greater than or equal to 0.20 and less than or equal to 1.00 within range. In an optional embodiment, the ratio G1/G2 of the gravimetric energy density G1 of the first type of cell to the gravimetric energy density G2 of the second type of cell may be within a range of greater than or equal to 0.30 and less than or equal to 0.99.
  • the ratio G1/G2 of the gravimetric energy density G1 of the first type of cell to the gravimetric energy density G2 of the second type of cell may be within a range of greater than or equal to 0.40 and less than or equal to 0.95.
  • the ratio G1/G2 may be, for example, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38 , 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63 , 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88 , 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.85, 0.86, 0.87
  • the energy density of the battery can affect the height, width, and/or thickness of the battery, and the design of the height, width, and/or thickness of the battery will in turn restrict the configuration of the energy density of the battery. This is described in more detail below.
  • the single cell of the first type since the energy density of the first type of cell is lower than that of the second type of cell, in order to obtain the same or similar capacity of a single cell, the single cell of the first type
  • the volume of the cell will be larger than that of a single cell of the second type of cell.
  • the existing first-type batteries with smaller volumes are still used for cost considerations.
  • the volume of a single cell (such as the height, width, and/or thickness of the cell) of the first type of cell differs too much from that of the second type of cell, it will be difficult for the production, assembly and use of each component of the battery module. will have an adverse effect.
  • the ratio V1/V2 of the volume V1 of each first-type cell to the volume V2 of each second-type cell can be controlled to be greater than 0.20 and less than Equal to the range of 20.00.
  • the ratio V1/V2 may be in the range of 0.40 or more and 5.00 or less.
  • the ratio V1/V2 may be within a range of 1.00 or more and 2.10 or less.
  • the ratio V1/V2 can be eg 0.21, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.00, 1.01, 1.02 , 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26 , 1.27 , 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52 , 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61, 1.62, 1.
  • the dimension along the direction of the mixed series connection of the two types of batteries can be defined as the thickness T of the battery cell, which is perpendicular to the top surface of the hybrid series battery module. Dimension is defined as the height H of the cell, and the remaining dimension is defined as the width W of the cell.
  • the ratio H1/H2 of the height H1 of the first type of battery cell to the height H2 of the second type of battery cell may be in the range of 0.9 ⁇ 1.1. In a preferred embodiment, the ratio H1/H2 may be equal to 1, that is, the heights of the first type of cells and the second type of cells are equal.
  • the ratio W1/W2 of the width W1 of the first type of cell to the width W2 of the second type of cell may be in the range of 0.9 ⁇ 1.1.
  • the ratio W1/W2 may be equal to 1, that is, the widths of the first type of cells and the second type of cells are equal.
  • the height and width of the first-type batteries and the second-type batteries are equal, which is more conducive to the production of various components of the battery module and improves production efficiency. It is also more conducive to the assembly of battery modules/battery packs, maximizing Greatly improve the space utilization rate and increase the volumetric energy density of the battery module/battery pack.
  • the ratio T1/T2 of the thickness T1 of the first type of cell to the thickness T2 of the second type of cell may be within a range greater than 1.00 and less than or equal to 20.00. In an optional implementation manner, the ratio T1/T2 of the thickness T1 of the first type of cell to the thickness T2 of the second type of cell may be within a range of greater than or equal to 1.02 and less than or equal to 5.00. In yet another optional embodiment, the ratio T1/T2 of the thickness T1 of the first type of cell to the thickness T2 of the second type of cell may be within a range of greater than or equal to 1.05 and less than or equal to 2.10.
  • the ratio T1/T2 may be, for example, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19 , 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44 , 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69 , 1.70, 1.71, 1.72, 1.73, 1.74, 1.75, 1.76, 1.77, 1.78, 1.79, 1.80
  • the volumes of the first type of cells and the second type of cells can be reasonably matched, so that It can optimize the space utilization of two types of batteries with different chemical systems, which is conducive to improving the volume energy density of batteries and battery modules/battery packs; at the same time, the capacity of single batteries can also be better matched, so that it can Optimize the power, life, power and high and low temperature performance of battery modules/battery packs.
  • the thickness of the cell with the lower energy density will be greater than the thickness of the cell with the higher energy density when the height and width of the two types of cells are basically the same much, in order to obtain the same or similar capacity as a higher energy density cell.
  • the thickness of the battery cell is too large, the heat dissipation performance of the battery cell is likely to deteriorate, and the manufacturability will also deteriorate, and the product yield will decrease, thereby deteriorating the processing and electrochemical performance of the battery cell.
  • a reasonable match between the energy density of the first type of battery and the second type of battery can promote a reasonable match between the two volumes (such as thickness), thereby ensuring that the single battery has better heat dissipation performance and can be manufactured industrially.
  • the battery modules/battery packs grouped in series have higher volumetric energy density and/or gravimetric energy density.
  • the porosity P1 of the first negative electrode sheet of the first type of cell is the same as that of the second negative electrode sheet of the second type of cell
  • the ratio P1/P2 of the porosity P2 may be in the range of 0.75 or more and 3.00 or less. In an optional embodiment, the ratio P1/P2 may be within a range of greater than or equal to 0.80 and less than or equal to 2.00. In yet another optional embodiment, the ratio P1/P2 may be within a range of greater than or equal to 0.90 and less than or equal to 1.50.
  • the ratio P1/P2 can be eg 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93 , 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18 , 1.19, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43 , 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.5
  • the porosity of one type of cell is too high and the porosity of the other type of cell is too low, resulting in a low density of the pole piece with too high porosity, and the contact with the electrolyte There are many interfaces. In order to fill all the pores, a large amount of electrolyte is required, and there are many side reactions at the interface, resulting in low energy density, high cost, poor cycle performance, large gas production, and increased expansion force of single cells and battery modules. larger. A cell with too low porosity may lead to poor infiltration of the electrolyte in the pole piece, thereby deteriorating the kinetics of the cell and affecting the capacity, rate and life of the cell. Therefore, it is advantageous to configure the porosity of the negative electrode sheets of the first type of cell and the second type of cell to be within the above range.
  • the average particle size S1 of the negative electrode active material of the first negative electrode sheet of the first type of battery cell is the same as the negative electrode active material of the second negative electrode sheet of the second type of battery cell
  • the ratio S1/S2 of the average particle size S2 may be in the range of 0.10 or more and less than 1.00.
  • the ratio S1/S2 of the average particle size S1 of the negative electrode active material of the first negative electrode sheet to the average particle size S2 of the negative electrode active material of the second negative electrode sheet can be greater than or equal to 0.15 and less than or equal to within the range of 0.95.
  • the ratio S1/S2 of the average particle size S1 of the negative electrode active material of the first negative electrode sheet to the average particle size S2 of the negative electrode active material of the second negative electrode sheet can be greater than or equal to 0.30 and less than equal to 0.90 in the range.
  • the ratio S1/S2 can be eg 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28 , 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52 , 0.53 , 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78 . It should be emphasized that although the above values are listed side by side in the present application, it does not mean that
  • the ratio S1/S2 is favorable within the above range, because it can make the average particle size of the negative electrode active material of the second type of battery larger than the average particle size of the negative electrode active material of the first type of battery, which is beneficial Improve the specific capacity of the material, improve the processing performance of the slurry, and increase the compaction density of the pole piece, thereby significantly increasing the energy density of the second type of battery, thereby increasing the energy density of the hybrid series battery module; in addition, it can also ensure The average particle size of the negative electrode active material of the first type of battery is relatively close to that of the second type of battery, which is conducive to maintaining the spatial structure of the pole piece, while suppressing the rebound of the pole piece, and maintaining a stable porosity during use. It is beneficial to the improvement of the cycle life of the battery cell and the cycle expansion force.
  • the ratio N/M of the number N of cells of the first type to the number M of cells of the second type may be greater than or equal to 1.
  • the ratio N/M of the number N of cells of the first type to the number M of cells of the second type may be within a range of greater than or equal to 1.5 and less than or equal to 200.
  • the ratio N/M of the number N of the first type of cells to the number M of the second type of cells may be within a range of greater than or equal to 2 and less than or equal to 100.
  • the ratio N/M can be eg 1.0, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 ,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90,95,100,105,110,115,120,125,130,135 , 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, etc. It should be emphasized that although the present application lists the above values in parallel, it does not mean that the inventors admit that the ratio N/M can obtain equivalent or similar performance within the value range formed by any two of the above values as endpoints.
  • the matching process of the number of the first type of cells and the second type of cells can be mainly from the difference in energy density, the difference in expansion force growth, the difference in dynamic performance, the difference in temperature rise, the difference in cost, and the safety performance. Different angles are designed. Within the above-mentioned range of the ratio N/M, the overall performance of the battery module is better.
  • the cells of the first type and the cells of the second type may be arranged at intervals.
  • the first type of cells may be arranged on the periphery, both ends and/or in the middle of the battery module/battery pack.
  • the cell arrangement method of this application can effectively reduce the local stress inside the battery module and improve the structural stability and safety of the battery module.
  • Figure 1A shows an exemplary cell arrangement for low energy density.
  • four cells of the first type with low energy density are arranged in the form of a quadrilateral.
  • Figure 1B shows an exemplary cell arrangement for high energy density.
  • a second type of high energy density cell is introduced, and similar to the example shown in Figure 1A, three low energy density first type cells are combined with a high energy density first type cell.
  • the second type of cells are mixed and arranged in the form of quadrilaterals.
  • the example in FIG. 1B improves the overall energy density of the obtained battery module due to the introduction of the second type of cells with high energy density.
  • Figure 1C shows an exemplary cell arrangement for high energy density, low stress, and high thermal insulation.
  • three first-type cells with low energy density and one second-type cell with high energy density are mixed and arranged in a triangle, and the three first-type cells connect the second
  • the second type of battery core is surrounded in the center, so that the obtained battery module has higher energy density, lower local stress and better high and low temperature performance.
  • Figure 2A and Figure 2B show the arrangement of an exemplary hybrid series battery module according to an embodiment of the present application, wherein the first digit of the battery cell number (such as "11" in Figure 2A) is The first type of battery is still the second type of battery, and the second number indicates the serial number, which is used to distinguish.
  • One set of battery modules is shown in Figure 2A, and six sets of battery modules are shown in Figure 2B.
  • one or more first-type batteries can be separated between the first-type batteries and the second-type batteries of the hybrid series battery module, for example, 2, 3, or 4 batteries can be separated , n battery cells of the first type.
  • the end cells of the battery module can be one or more first-type cells, one or more second-type cells, or one first-type cell and one second-type cell. Batteries.
  • the position of the second type of battery cells may be at the end of the battery module or at other positions, or occupy both the end of the battery module and other positions except the end.
  • Table 1 and Table 2 show 9 examples of the present application, and show 3 comparative examples as controls.
  • Table 1 can show the ratio d1/d2 of the layer spacing d1 of the negative electrode active material of the first negative electrode sheet of the first type of battery to the layer spacing d2 of the negative electrode active material of the second negative electrode sheet of the second type of battery The influence of the expansion force of the battery module during repeated charging and discharging.
  • Table 2 can show the ratio S1/ The influence of S2 on the capacity retention rate of the battery module. Capacity retention is associated with the cycle life of the cell. Under the same conditions, the higher the capacity retention rate, the longer the cycle life of the cells in the battery module.
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the present application has no specific limitation on the type of electrolyte, which can be selected according to requirements.
  • electrolytes can be liquid, gel or all solid.
  • the electrolyte is an electrolytic solution.
  • the electrolytic solution includes an electrolytic salt and a solvent.
  • the electrolyte salt may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide, At least one of lithium fluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium difluorooxalate borate, lithium difluorodifluorooxalatephosphate and lithium tetrafluorooxalatephosphate.
  • the solvent may be selected from ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethylene propylene carbonate ester, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, butyl At least one of ethyl acetate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte also optionally includes additives.
  • additives can include negative film-forming additives, positive film-forming additives, and additives that can improve certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high-temperature or low-temperature performance of the battery, and the like.
  • the cell further includes an isolation film.
  • the present application has no particular limitation on the type of the isolation membrane, and any known porous structure isolation membrane with good chemical stability and mechanical stability can be selected.
  • the material of the isolation film can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride.
  • the separator can be a single-layer film or a multi-layer composite film, without any particular limitation. When the separator is a multilayer composite film, the materials of each layer may be the same or different, and there is no particular limitation.
  • the positive pole piece, the negative pole piece and the separator can be made into an electrode assembly through a winding process or a lamination process.
  • NMP N-methylpyrrolidone
  • Negative electrode active material such as graphite and conductive carbon, binder polystyrene butadiene copolymer (SBR), thickener sodium carboxymethyl cellulose (CMC) are in water solvent by 96.6:0.8:1.8:0.8 weight ratio Fully stir and mix in the medium to form a uniform negative electrode stable slurry; this slurry is evenly coated on the negative electrode current collector Cu foil with a coating amount of 11mg/cm 2 , and after drying, the electrode sheet is cold pressed to the design pressure Encrypted, divided into spare parts.
  • SBR binder polystyrene butadiene copolymer
  • CMC thickener sodium carboxymethyl cellulose
  • PE polyethylene
  • PP polypropylene
  • the positive pole piece, the separator and the negative pole piece are wound together into a bare battery cell, then placed in the battery case, injected with electrolyte, followed by formation, sealing and other processes, and finally obtained Rechargeable power cells.
  • the battery cell may include an outer package for encapsulating the above-mentioned electrode assembly and electrolyte.
  • the outer package of the battery cell may be a soft bag, such as a bag-type soft bag.
  • the material of the soft bag can be plastic, such as one or more of polypropylene PP, polybutylene terephthalate PBT, polybutylene succinate PBS, and the like.
  • the outer packaging of the battery cell can also be a hard shell, such as a hard plastic shell, aluminum shell, steel shell, etc.
  • an outer package may include a housing and a cover.
  • the casing may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose to form an accommodating cavity.
  • the casing has an opening communicating with the accommodating cavity, and the cover plate can cover the opening to close the accommodating cavity.
  • the positive electrode sheet, the negative electrode sheet and the separator can be laminated or wound to form a laminated structure electrode assembly or a wound structure electrode assembly.
  • the electrode assembly is packaged in the accommodating cavity.
  • the electrolyte can be an electrolytic solution, and the electrolytic solution is infiltrated in the electrode assembly.
  • two or more battery modules can be Assembled into a battery pack.
  • the number of battery modules contained in a battery pack depends on the application of the battery pack and the parameters of a single battery module.
  • the battery pack may include a battery box (as shown in FIGS. 3A-3C ) and a plurality of battery modules disposed in the battery box.
  • the battery box includes an upper box and a lower box. The upper box can cover and cooperate with the lower box to form a closed space for accommodating the battery module. Two or more battery modules can be arranged in the battery box in a desired manner.
  • a “battery pack” is made of one or more battery modules (or a combination directly formed by multiple cells) and further equipped with various control and protection systems such as a battery management system and a thermal management system (As shown in Figures 4A-4C).

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Abstract

本申请涉及混合串联电池模组、电池包以及用电装置。该混合串联电池模组包括：一个或多个第一类电芯，每一个第一类电芯包括第一负极极片；以及一个或多个第二类电芯，每一个第二类电芯包括第二负极极片；其中第一类电芯的能量密度小于第二类电芯的能量密度，并且其中第一负极极片的负极活性物质的层间距d1大于第二负极极片的负极活性物质的层间距d2，并且在0％荷电状态下，层间距d1与层间距d2的比值d1/d2在大于等于1.005且小于等于1.600的范围内。

Description

混合串联电池模组、电池包以及用电装置 技术领域
1.本申请涉及二次电池技术领域，更具体地，本申请涉及混合串联电池模组、电池包以及用电装置。
背景技术
2.在二次电池领域，与锂离子电池相比，诸如钠离子电池和钾离子电池等其他电池由于在关键的电化学性能能量密度方面表现较弱使得续航能力较差，因此本领域技术人员普遍认为钠离子电池和钾离子电池等不太适用于工业应用。在数十年的发展中，本领域技术人员基本上集中于对锂离子电池的研究，而忽视了钠离子电池和钾离子电池。
3.锂离子电池广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。由于锂离子电池取得了极大的发展，因此对其能量密度、循环性能和安全性能等的提升也提出了更高的要求。然而，近几年锂离子电池的技术发展出现了瓶颈期。同时，由于锂资源价格的上涨，使得锂离子电池的成本上升。
4.因此，本领域中存在对改进的电池模组的需要。
发明内容
5.本申请是鉴于上述课题而进行的，其目的在于，提供一种改进的电池模组以及包括该改进的电池模组的电池包和用电装置。具体地，本申请将诸如钠离子电池或钾离子电池之类的第一类电芯与诸如锂离子电池之类的第二类电芯进行适当的混合排布，使得第一类电芯和第二类电芯能够在性能方面优势互补，从而提升了电池模组的综合性能，包括但不限于例如能量密度、低温性能、结构稳定性、安全性、散热性能、工业可制造性等，同时降低了电池模组的整 体成本。
6.然而，由于第一类电芯与第二类电芯使用了不同的化学体系，因此在对第一类电芯和第二类电芯进行混合排布(例如，串联)时，往往会在二者的兼容性和配合性方面出现诸多的问题，使得所获得的电池模组的性能没有提升，甚至反而劣化，直至使得电池模组失效。本领域技术人员一直期望解决这方面的问题而不得。本申请主要通过对电芯的负极活性物质的层间距进行匹配设计创造性地解决了该问题，从而获得性能改善的电池模组。
7.本申请的第一方面提供了一种混合串联电池模组，该混合串联电池模组包括：一个或多个第一类电芯，每一个所述第一类电芯包括第一负极极片；以及一个或多个第二类电芯，每一个所述第二类电芯包括第二负极极片。所述第一类电芯的能量密度小于所述第二类电芯的能量密度。所述第一负极极片的负极活性物质的层间距d1大于所述第二负极极片的负极活性物质的层间距d2。在0％荷电状态下，所述层间距d1与所述层间距d2的比值d1/d2在大于等于1.005且小于等于1.600的范围内。
8.在任意实施方式中，可选地，在0％荷电状态下，所述层间距d1与所述层间距d2的比值d1/d2在大于等于1.010且小于等于1.200的范围内。进一步可选地，在0％荷电状态下，所述层间距d1与所述层间距d2的比值d1/d2在大于等于1.100且小于等于1.170的范围内。
9.在任意实施方式中，所述第一类电芯的能量密度与所述第二类电芯的能量密度相匹配使得所述第一类电芯的体积V1与所述第二类电芯的体积V2的比值V1/V2在大于0.20且小于等于20.00的范围内。可选地，所述第一类电芯的能量密度与所述第二类电芯的能量密度相匹配使得所述第一类电芯的体积V1与所述第二类电芯的体积V2的比值V1/V2在大于等于0.40且小于等于5.00的范围内。进一步可选地，所述第一类电芯的能量密度与所述第二类电芯的能量密度相匹配使得所述第一类电芯的体积V1与所述第二类电芯的体积V2的比值V1/V2在大于等于1.00且小于等于2.10的范围内。
10.在任意实施方式中，所述第一类电芯的能量密度与所述第二类电芯的能量密度相匹配使得所述第一类电芯的厚度T1与所述第二类电芯的厚度T2的比 值T1/T2在大于1.00且小于等于20.00的范围内。可选地，所述第一类电芯的能量密度与所述第二类电芯的能量密度相匹配使得所述第一类电芯的厚度T1与所述第二类电芯的厚度T2的比值T1/T2在大于等于1.02且小于等于5.00的范围内。进一步可选地，所述第一类电芯的能量密度与所述第二类电芯的能量密度相匹配使得所述第一类电芯的厚度T1与所述第二类电芯的厚度T2的比值T1/T2在大于等于1.05且小于等于2.10的范围内。
11.在任意实施方式中，所述第一类电芯的体积能量密度E1与所述第二类电芯的体积能量密度E2的比值E1/E2在大于等于0.20且小于等于1.00的范围内。可选地，所述第一类电芯的体积能量密度E1与所述第二类电芯的体积能量密度E2的比值E1/E2在大于等于0.25且小于等于0.90的范围内。进一步可选地，所述第一类电芯的体积能量密度E1与所述第二类电芯的体积能量密度E2的比值E1/E2在大于等于0.30且小于等于0.86的范围内。
12.在任意实施方式中，所述第一类电芯的重量能量密度G1与所述第二类电芯的重量能量密度G2的比值G1/G2在大于等于0.20且小于等于1.00的范围内。可选地，所述第一类电芯的重量能量密度G1与所述第二类电芯的重量能量密度G2的比值G1/G2在大于等于0.30且小于等于0.99的范围内。进一步可选地，所述第一类电芯的重量能量密度G1与所述第二类电芯的重量能量密度G2的比值G1/G2在大于等于0.40且小于等于0.95的范围内。
13.在任意实施方式中，在不包括基材的情况下，所述第一负极极片的孔隙率P1与所述第二负极极片的孔隙率P2的比值P1/P2在大于等于0.75且小于等于3.00的范围内。可选地，在不包括基材的情况下，所述第一负极极片的孔隙率P1与所述第二负极极片的孔隙率P2的比值P1/P2在大于等于0.80且小于等于2.00的范围内。进一步可选地，在不包括基材的情况下，所述第一负极极片的孔隙率P1与所述第二负极极片的孔隙率P2的比值P1/P2在大于等于0.90且小于等于1.50的范围内。
14.在任意实施方式中，所述第一负极极片的负极活性物质的平均粒径S1与所述第二负极极片的负极活性物质的平均粒径S2的比值S1/S2在大于等于0.10且小于1.00的范围内。可选地，所述第一负极极片的负极活性物质的平均 粒径S1与所述第二负极极片的负极活性物质的平均粒径S2的比值S1/S2在大于等于0.15且小于等于0.95的范围内。进一步可选地，所述第一负极极片的负极活性物质的平均粒径S1与所述第二负极极片的负极活性物质的平均粒径S2的比值S1/S2在大于等于0.30且小于等于0.90的范围内。
15.在任意实施方式中，所述第一类电芯的数量N与所述第二类电芯的数量M的比值N/M大于等于1。可选地，所述第一类电芯的数量N与所述第二类电芯的数量M的比值N/M在大于等于1.5且小于等于200的范围内。进一步可选地，所述第一类电芯的数量N与所述第二类电芯的数量M的比值N/M在大于等于2且小于等于100的范围内。
16.在任意实施方式中，所述第一类电芯与所述第二类电芯间隔排布。
17.在任意实施方式中，所述第一类电芯被排布在所述混合串联电池模组的两端和中间。
18.本申请的第二方面提供了一种电池包。该电池包包括本申请第一方面的混合串联电池模组。
19.本申请的第三方面提供了一种用电装置。该用电装置包括本申请第一方面的混合串联电池模组或本申请第二方面的电池包。
附图说明
20.为了能够详细地理解本发明，可参考实施方式得出上文所简要概述的本发明的更具体的描述，一些实施方式在附图中示出，为了促进理解，已尽可能使用相同附图标记来标示各图所共有的相同要素。然而，应当注意，附图仅仅示出本发明的典型实施方式，并且因此不应视为限制本发明的范围，因为本发明可允许其他等效实施方式，其中：
21.图1A示出了一种低能量密度的示例性电芯排布方式。
22.图1B示出了一种高能量密度的示例性电芯排布方式。
23.图1C示出了一种高能量密度、低应力且高保温的示例性电芯排布方式。
24.图2A和图2B示出了根据本申请的实施方式的示例性混合串联电池 模组的排布方式。
25.图3A示出了根据本申请的实施方式的用于电池包的示例性电池箱的下箱体的立体图。
26.图3B示出了图3A的示例性电池箱的上箱体的俯视图。
27.图3C示出了沿着图3B中的线A－A截取的示意性截面图。
28.图4A示出了根据本申请的实施方式的一种示例性电池包的立体图。
29.图4B示出了图4A的示例性电池包的顶视图。
30.图4C示出了沿着图4B中的线B－B截取的示意性截面图。
具体实施方式
31.以下，适当地参照附图详细说明具体公开了本申请的正极活性材料及其制造方法、正极极片、二次电池、电池模块、电池包和电学装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
32.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。
33.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。
34.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。
35.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。
36.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。
37.在本文的描述中，需要说明的是，除非另有说明，“以上”、“以下”为包含本数，“一种或几种”中“几种”的含义是两种及两种以上。
38.在本文的描述中，除非另有说明，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)。
39.此外，还可以理解的是，附图中示出的各种实施方式是说明性的，且附图不一定按比例绘制。
40.本申请使用了特定词语来描述本申请的实施方式。如“一个实施方式”、“一实施方式”、和/或“一些实施方式”意指与本申请至少一个实施方式相关的某一特征、结构或特点。因此，应强调并注意的是，本说明书中在不同位置两次或多次提及的“一实施方式”或“一个实施方式”或“一替代性实施方式”并不一定是指同一实施方式。此外，本申请的一个或多个实施方式中的某些特征、结构或特点可以进行适当的组合。
41.在本文中，除非另作定义，权利要求书和说明书中使用的技术术语或者科学术语应当为本发明所属技术领域的普通技术人员所理解的通常意义。本申请说明书以及权利要求书中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。“一个”或者“一”等类似词语并不表示数量限制，而是表示存在至少一个。
42.在本申请中，“电芯”是指能够独立进行充放电的电池单体。本申请对电芯的形状没有限制，其可以是圆柱形、方形或其他任意的形状。
43.在混合串联电池模组中，第一类电芯(诸如钠离子电芯、钾离子电芯)和第二类电芯(诸如锂离子电芯)由于使用了不同的化学体系，因此进行可逆脱嵌的活性离子的半径不同，脱嵌机理也有差异，两类电芯在进行混合排布时互相制约，往往会出现矛盾之处，在性能方面顾此失彼，使得混合排布所得的电池模组的性能反而可能下降，甚至使得电池模组失效。本领域技术人员一直期望将混合串联电池模组中的两类不同电芯在性能上的顾此失彼转变为优势互补，但在本申请之前一直未找到克服两类不同电芯之间的这种制约和矛盾的方法。
44.发明人注意到，当电芯负极极片中的负极活性物质的层间距越小时，允许嵌入层间的活性离子的半径越小，活性离子从层间结构脱嵌时的难度更大，并且因此动力学较差。层间距小的活性物质，结晶度(亦即，晶体结构的长程有序度)高，各向异性强，导致极片反弹较大，电芯在反复充放电过程中膨胀力增加较快。当电芯负极极片中的负极活性物质的层间距越大时，允许嵌入层间的活性离子的半径越大，活性离子从层间结构脱嵌时更容易，并且因此动力学较好。层间距大的活性物质，结晶度(亦即，晶体结构的长程有序度)低，各向同性强，导致极片反弹较小，电芯在反复充放电过程中膨胀力增加较慢。在本申请中，第一类电芯的负极活性物质的层间距d1大于第二类电芯的负极活性物质的层间距d2。
45.因此，第一类电芯和第二类电芯的负极活性物质的层间距之间的匹配程度对成组后的电池模组/电池包的性能可能产生极大影响。本申请采用第一类电芯的负极活性物质的层间距d1与第二类电芯的负极活性物质的层间距d2 之间的比值d1/d2来表示这种匹配程度，并利用这种匹配程度成功地使得第一类电芯和第二类电芯的性能互补，从而提高了所获得的电池模组的整体性能。
46.在一个实施方式中，本申请提出了一种混合串联电池模组，该混合串联电池模组可以包括一个或多个第一类电芯和一个或多个第二类电芯，其中每一个第一类电芯可包括第一负极极片，且每一个第二类电芯可包括第二负极极片。第一类电芯的能量密度可以小于第二类电芯的能量密度。第一负极极片的负极活性物质的层间距d1可以大于第二负极极片的负极活性物质的层间距d2。在0％荷电状态(SOC)下，即当可脱嵌的活性离子完全从负极脱出以后，层间距d1与层间距d2的比值d1/d2可以是在大于等于1.005且小于等于1.600的范围内。
47.如果d1/d2超出了上述范围，则可能造成第一类电芯的活性离子无法嵌入负极活性物质，或者第一类电芯和第二类电芯嵌入负极活性物质的活性离子较少，导致电池模组的容量较低、倍率性能较差。与之相反，如果d1/d2在上述范围内，则所得到的电池模组的容量相对较高、倍率性能较好。同时，在上述范围内，d1与d2相对比较接近，这有利于改善电池模组的整体动力学性能和电芯反复充放电过程中膨胀力的增加。特别是针对电池模组的电芯膨胀力的增加，由于两类电芯的化学体系差异，要减少膨胀力的增加十分困难。
48.在可选的实施方式中，在0％荷电状态下，层间距d1与层间距d2的比值d1/d2可以是在大于等于1.010且小于等于1.200的范围内。另外地或替代地，在0％荷电状态下，层间距d1与层间距d2的比值d1/d2可以是在大于等于1.100且小于等于1.170的范围内。举例而言，比值d1/d2可以是例如1.005、1.010、1.015、1.020、1.025、1.030、1.035、1.040、1.045、1.050、1.055、1.060、1.065、1.070、1.075、1.080、1.085、1.090、1.095、1.100、1.105、1.110、1.115、1.120、1.125、1.130、1.135、1.140、1.145、1.150、1.155、1.160、1.165、1.170、1.175、1.180、1.185、1.190、1.195、1.200、1.205、1.210、1.215、1.220、1.225、1.230、1.235、1.240、1.245、1.250、1.255、1.260、1.265、1.270、1.275、1.280、1.285、1.290、1.295、1.300、1.305、1.310、1.315、1.320、1.325、1.330、1.335、1.340、1.345、1.350、1.355、1.360、1.365、1.370、1.375、1.380、1.385、1.390、 1.395、1.400、1.405、1.410、1.415、1.420、1.425、1.430、1.435、1.440、1.445、1.450、1.455、1.460、1.465、1.470、1.475、1.480、1.485、1.490、1.495、1.500、1.505、1.510、1.515、1.520、1.525、1.530、1.535、1.540、1.545、1.550、1.555、1.560、1.565、1.570、1.575、1.580、1.585、1.590、1.595、1.600，等等。需要强调的是，虽然本申请将上述数值并列地列出，但是并不意味着发明人承认比值d1/d2在上述任意两个数值作为端点组成的数值范围内都可以得到相当或相近的性能。
49.本申请中电芯的负极活性物质的层间距d的测试方法为：参考国标GB/T-31486先将电芯完全放电至放电终止电压，并静置。将电芯拆解后，取出负极极片。将负极极片在DMC中浸泡24小时，取出，用DMC冲洗后，烘干待测。使用X射线衍射仪例如Bruker D8 Discover，并使用Cu Kα1(波长0.154056nm)测试负极极片，得到极片的X射线衍射谱图。读取(002)峰对应的2θ位置(25～28°)，根据所用入射波的波长λ及布拉格公式2dsinθ＝nλ计算(002)峰对应的层间距d。
50.在本申请的一个实施方式中，第一类电芯可以是钠离子电池化学体系，包括但不限于：普鲁士蓝类衍生物/硬炭体系、聚阴离子型快离子导体磷酸钒钠(或者氟磷酸钒钠、氟氧磷酸钒钠)/硬炭体系、过渡金属氧化物/硬炭体系等；而第二类电芯可以是使用橄榄石结构的活性物质作为主要正极材料的电芯(例如LiFePO 4、LiMn 0.6Fe 0.4PO 4)、使用层状结构的镍钴锰酸锂为主要正极材料的电芯(例如LiNi 0.60Co 0.10Mn 0.30O 2)等。
51.本申请还可以通过以下进一步的优化设计，显著提升了单体电芯和电池模组的动力学性能，有效降低了电池模组内部的局部应力，改善了电池模组的结构稳定性和安全性等。
52. 电芯能量密度
53.电芯的能量密度可以是体积能量密度或重量能量密度。在本申请中，第一类电芯的能量密度小于第二类电芯的能量密度。在一示例中，第一类电芯的体积能量密度E1可以在例如200至450Wh/L的范围内。在一示例中，第二类电芯的体积能量密度E2可以在例如450至750Wh/L的范围内。在一示例中， 第一类电芯的重量能量密度G1可以在例如100至220Wh/Kg的范围内。在一示例中，第二类电芯的重量能量密度G2可以在例如220至350Wh/Kg的范围内。
54.在本申请的一个或多个实施方式中，第一类电芯的体积能量密度E1与第二类电芯的体积能量密度E2的比值E1/E2可以在大于等于0.20且小于等于1.00的范围内。在一可选实施方式中，第一类电芯的体积能量密度E1与第二类电芯的体积能量密度E2的比值E1/E2可以在大于等于0.25且小于等于0.90的范围内。在又一可选实施方式中，第一类电芯的体积能量密度E1与第二类电芯的体积能量密度E2的比值E1/E2可以在大于等于0.30且小于等于0.86的范围内。
55.举例而言，比值E1/E2可以是例如0.20、0.21、0.22、0.23、0.24、0.25、0.26、0.27、0.28、0.29、0.30、0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.40、0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.50、0.51、0.52、0.53、0.54、0.55、0.56、0.57、0.58、0.59、0.60、0.61、0.62、0.63、0.64、0.65、0.66、0.67、0.68、0.69、0.70、0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.80、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.90、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1.00，等等。需要强调的是，虽然本申请将上述数值并列地列出，但是并不意味着发明人承认比值E1/E2在上述任意两个数值作为端点组成的数值范围内都可以得到相当或相近的性能。
56.在本申请的一个或多个实施方式中，第一类电芯的重量能量密度G1与第二类电芯的重量能量密度G2的比值G1/G2可以在大于等于0.20且小于等于1.00的范围内。在一可选实施方式中，第一类电芯的重量能量密度G1与第二类电芯的重量能量密度G2的比值G1/G2可以在大于等于0.30且小于等于0.99的范围内。在又一可选实施方式中，第一类电芯的重量能量密度G1与第二类电芯的重量能量密度G2的比值G1/G2可以在大于等于0.40且小于等于0.95的范围内。
57.举例而言，比值G1/G2可以是例如0.20、0.21、0.22、0.23、0.24、 0.25、0.26、0.27、0.28、0.29、0.30、0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.40、0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.50、0.51、0.52、0.53、0.54、0.55、0.56、0.57、0.58、0.59、0.60、0.61、0.62、0.63、0.64、0.65、0.66、0.67、0.68、0.69、0.70、0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.80、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.90、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1.00，等等。需要强调的是，虽然本申请将上述数值并列地列出，但是并不意味着发明人承认比值G1/G2在上述任意两个数值作为端点组成的数值范围内都可以得到相当或相近的性能。
58.电芯的能量密度可以影响电芯的高度、宽度、和/或厚度，而对电芯的高度、宽度、和/或厚度的设计也会反过来制约对电芯的能量密度的配置，这会在下文中更详细地描述。
59. 电芯高度、宽度、厚度
60.在本申请的优选实施方式中，由于第一类电芯的能量密度比第二类电芯的能量密度低，因此为了获得相同或相近的单个电芯容量，第一类电芯的单个电芯体积会比第二类电芯的单个电芯体积大。在另一些实施方式中，鉴于现有的生产设施和技术等因素，出于成本考虑，仍然使用现有的体积较小的第一类电芯。但是，如果第一类电芯与第二类电芯的单个电芯体积(诸如电芯的高度、宽度、和/或厚度)相差太多，对于电池模组各部件的生产、装配和使用均会产生不利影响。
61.因此，在本申请的一个或多个实施方式中，每个第一类电芯的体积V1与每个第二类电芯的体积V2的比值V1/V2可以被控制在大于0.20且小于等于20.00的范围内。在可选实施方式中，比值V1/V2可以在大于等于0.40且小于等于5.00的范围内。在优选的实施方式中，比值V1/V2可以在大于等于1.00且小于等于2.10的范围内。
62.举例而言，比值V1/V2可以是例如0.21、0.25、0.30、0.35、0.40、0.45、0.50、0.55、0.60、0.65、0.70、0.75、0.80、0.85、0.90、0.95、1.00、1.01、1.02、1.03、1.04、1.05、1.06、1.07、1.08、1.09、1.10、1.11、1.12、1.13、1.14、 1.15、1.16、1.17、1.18、1.19、1.20、1.21、1.22、1.23、1.24、1.25、1.26、1.27、1.28、1.29、1.30、1.31、1.32、1.33、1.34、1.35、1.36、1.37、1.38、1.39、1.40、1.41、1.42、1.43、1.44、1.45、1.46、1.47、1.48、1.49、1.50、1.51、1.52、1.53、1.54、1.55、1.56、1.57、1.58、1.59、1.60、1.61、1.62、1.63、1.64、1.65、1.66、1.67、1.68、1.69、1.70、1.71、1.72、1.73、1.74、1.75、1.76、1.77、1.78、1.79、1.80、1.81、1.82、1.83、1.84、1.85、1.86、1.87、1.88、1.89、1.90、1.91、1.92、1.93、1.94、1.95、1.96、1.97、1.98、1.99、2.00、2.01、2.02、2.03、2.04、2.05、2.06、2.07、2.08、2.09、2.10、2.20、2.30、2.40、2.50、2.60、2.70、2.80、2.90、3.00、3.10、3.20、3.30、3.40、3.50、3.60、3.70、3.80、3.90、4.00、4.10、4.20、4.30、4.40、4.50、4.60、4.70、4.80、4.90、5.00、5.50、6.00、6.50、7.00、7.50、8.00、8.50、9.00、9.50、10.00、10.50、11.00、11.50、12.00、12.50、13.00、13.50、14.00、14.50、15.00、15.50、16.00、16.50、17.00、17.50、18.00、18.50、19.00、19.50、20.00，等等。需要强调的是，虽然本申请将上述数值并列地列出，但是并不意味着发明人承认比值V1/V2在上述任意两个数值作为端点组成的数值范围内都可以得到相当或相近的性能。
63.就电芯的高度、宽度、厚度而言，在本文中可以将沿着两类电芯混合串联方向的维度定义为电芯的厚度T，将与混合串联电池模组的顶面垂直的维度定义为电芯的高度H，并将余下的一个维度定义为电芯的宽度W。
64.在本申请的实施方式中，第一类电芯的高度H1与第二类电芯的高度H2的比值H1/H2可以在0.9～1.1的范围内。在优选的实施方式中，比值H1/H2可以等于1，即，第一类电芯与第二类电芯的高度相等。
65.类似地，第一类电芯的宽度W1与第二类电芯的宽度W2的比值W1/W2可以在0.9～1.1的范围内。在优选的实施方式中，比值W1/W2可以等于1，即，第一类电芯与第二类电芯的宽度相等。
66.第一类电芯与第二类电芯的高度和宽度相等，更有利于电池模组各部件的生产、提高生产效率，同时也更有利于电池模组/电池包的装配，最大化地提升空间利用率，提高电池模组/电池包的体积能量密度。
67.接下来讨论的是第一类电芯和第二类电芯的厚度。在实施方式中， 第一类电芯的厚度T1与第二类电芯的厚度T2的比值T1/T2可以在大于1.00且小于等于20.00的范围内。在一可选实施方式中，第一类电芯的厚度T1与第二类电芯的厚度T2的比值T1/T2可以在大于等于1.02且小于等于5.00的范围内。在又一可选实施方式中，第一类电芯的厚度T1与第二类电芯的厚度T2的比值T1/T2可以在大于等于1.05且小于等于2.10的范围内。
68.举例而言，比值T1/T2可以是例如1.01、1.02、1.03、1.04、1.05、1.06、1.07、1.08、1.09、1.10、1.11、1.12、1.13、1.14、1.15、1.16、1.17、1.18、1.19、1.20、1.21、1.22、1.23、1.24、1.25、1.26、1.27、1.28、1.29、1.30、1.31、1.32、1.33、1.34、1.35、1.36、1.37、1.38、1.39、1.40、1.41、1.42、1.43、1.44、1.45、1.46、1.47、1.48、1.49、1.50、1.51、1.52、1.53、1.54、1.55、1.56、1.57、1.58、1.59、1.60、1.61、1.62、1.63、1.64、1.65、1.66、1.67、1.68、1.69、1.70、1.71、1.72、1.73、1.74、1.75、1.76、1.77、1.78、1.79、1.80、1.81、1.82、1.83、1.84、1.85、1.86、1.87、1.88、1.89、1.90、1.91、1.92、1.93、1.94、1.95、1.96、1.97、1.98、1.99、2.00、2.01、2.02、2.03、2.04、2.05、2.06、2.07、2.08、2.09、2.10、2.20、2.30、2.40、2.50、2.60、2.70、2.80、2.90、3.00、3.10、3.20、3.30、3.40、3.50、3.60、3.70、3.80、3.90、4.00、4.10、4.20、4.30、4.40、4.50、4.60、4.70、4.80、4.90、5.00、5.50、6.00、6.50、7.00、7.50、8.00、8.50、9.00、9.50、10.00、10.50、11.00、11.50、12.00、12.50、13.00、13.50、14.00、14.50、15.00、15.50、16.00、16.50、17.00、17.50、18.00、18.50、19.00、19.50、20.00，等等。需要强调的是，虽然本申请将上述数值并列地列出，但是并不意味着发明人承认比值T1/T2在上述任意两个数值作为端点组成的数值范围内都可以得到相当或相近的性能。
69.通过对上述比值中的一个或多个比值进行配置，第一类电芯与第二类电芯的体积(包括电芯的高度、宽度、和/或厚度)可被合理地匹配，使得能够优化两类不同化学体系的电芯的空间利用率，有利于提升电芯以及电池模组/电池包的体积能量密度；同时，单体电芯的容量也可以更好地匹配，从而使得能够优化电池模组/电池包的电量、寿命、功率以及高低温性能等。
70.另一方面，对第一类电芯与第二类电芯的能量密度进行合理地匹配 也可以促进二者体积的合理匹配。如果两类电芯的能量密度差异过大，则在两类电芯的高度和宽度基本上一致的情况下，能量密度较低的电芯的厚度会比能量密度较高的电芯的厚度大得多，以便获得与能量密度较高的电芯相同或相近的容量。然而，如果电芯的厚度过大，电芯的散热性能很可能会变差，并且可制造性也会变差，产品优率降低，从而使得电芯的加工和电化学性能恶化。反过来，第一类电芯与第二类电芯的能量密度的合理匹配可以促进二者体积(诸如厚度)的合理匹配，从而在保证单体电芯具有较好的散热性能且可工业化制造的同时，使得串联成组后的电池模组/电池包具有更高的体积能量密度和/或重量能量密度。
71. 负极极片孔隙率
72.在本申请的一个或多个实施方式中，在不包括基材的情况下，第一类电芯的第一负极极片的孔隙率P1与第二类电芯的第二负极极片的孔隙率P2的比值P1/P2可以在大于等于0.75且小于等于3.00的范围内。在一可选实施方式中，该比值P1/P2可以在大于等于0.80且小于等于2.00的范围内。在又一可选实施方式中，该比值P1/P2可以在大于等于0.90且小于等于1.50的范围内。
73.举例而言，比值P1/P2可以是例如0.75、0.76、0.77、0.78、0.79、0.80、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.90、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1.00、1.01、1.02、1.03、1.04、1.05、1.06、1.07、1.08、1.09、1.10、1.11、1.12、1.13、1.14、1.15、1.16、1.17、1.18、1.19、1.20、1.21、1.22、1.23、1.24、1.25、1.26、1.27、1.28、1.29、1.30、1.31、1.32、1.33、1.34、1.35、1.36、1.37、1.38、1.39、1.40、1.41、1.42、1.43、1.44、1.45、1.46、1.47、1.48、1.49、1.50、1.51、1.52、1.53、1.54、1.55、1.56、1.57、1.58、1.59、1.60、1.61、1.62、1.63、1.64、1.65、1.66、1.67、1.68、1.69、1.70、1.71、1.72、1.73、1.74、1.75、1.76、1.77、1.78、1.79、1.80、1.81、1.82、1.83、1.84、1.85、1.86、1.87、1.88、1.89、1.90、1.91、1.92、1.93、1.94、1.95、1.96、1.97、1.98、1.99、2.00、2.01、2.02、2.03、2.04、2.05、2.06、2.07、2.08、2.09、2.10、2.11、2.12、2.13、2.14、2.15、2.16、2.17、2.18、2.19、2.20、2.21、2.22、 2.23、2.24、2.25、2.26、2.27、2.28、2.29、2.30、2.31、2.32、2.33、2.34、2.35、2.36、2.37、2.38、2.39、2.40、2.41、2.42、2.43、2.44、2.45、2.46、2.47、2.48、2.49、2.50、2.51、2.52、2.53、2.54、2.55、2.56、2.57、2.58、2.59、2.60、2.61、2.62、2.63、2.64、2.65、2.66、2.67、2.68、2.69、2.70、2.71、2.72、2.73、2.74、2.75、2.76、2.77、2.78、2.79、2.80、2.81、2.82、2.83、2.84、2.85、2.86、2.87、2.88、2.89、2.90、2.91、2.92、2.93、2.94、2.95、2.96、2.97、2.98、2.99、3.00，等等。需要强调的是，虽然本申请将上述数值并列地列出，但是并不意味着发明人承认比值P1/P2在上述任意两个数值作为端点组成的数值范围内都可以得到相当或相近的性能。
74.当上述孔隙率比值过大时，一类电芯的孔隙率过高而另一类电芯的孔隙率过低，造成孔隙率过高的极片压密较低，与电解液接触的界面较多。为了填充所有孔隙，需要的电解液的量较大，界面的副反应多，从而导致单体电芯及电池模组的能量密度低、成本高、循环性能恶化、产气较大、膨胀力增长较大。孔隙率过低的电芯，则可能导致电解液在极片中的浸润较差，从而恶化电芯的动力学，影响电芯的容量、倍率及寿命。因此，将第一类电芯与第二类电芯的负极极片孔隙率配置成介于上述范围内是有利的。
75. 负极活性物质平均粒径
76.在本申请的一个或多个实施方式中，第一类电芯的第一负极极片的负极活性物质的平均粒径S1与第二类电芯的第二负极极片的负极活性物质的平均粒径S2的比值S1/S2可以在大于等于0.10且小于1.00的范围内。在一可选实施方式中，第一负极极片的负极活性物质的平均粒径S1与第二负极极片的负极活性物质的平均粒径S2的比值S1/S2可以在大于等于0.15且小于等于0.95的范围内。在又一可选实施方式中，第一负极极片的负极活性物质的平均粒径S1与第二负极极片的负极活性物质的平均粒径S2的比值S1/S2可以在大于等于0.30且小于等于0.90的范围内。
77.举例而言，比值S1/S2可以是例如0.10、0.11、0.12、0.13、0.14、0.15、0.16、0.17、0.18、0.19、0.20、0.21、0.22、0.23、0.24、0.25、0.26、0.27、0.28、0.29、0.30、0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.40、 0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.50、0.51、0.52、0.53、0.54、0.55、0.56、0.57、0.58、0.59、0.60、0.61、0.62、0.63、0.64、0.65、0.66、0.67、0.68、0.69、0.70、0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.80、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.90、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98、0.99，等等。需要强调的是，虽然本申请将上述数值并列地列出，但是并不意味着发明人承认比值S1/S2在上述任意两个数值作为端点组成的数值范围内都可以得到相当或相近的性能。
78.比值S1/S2在上述范围内是有利的，因为这样可以使得第二类电芯的负极活性物质的平均粒径比第一类电芯的负极活性物质的平均粒径大，这有利于提高材料的比容量，同时改善浆料的加工性能，提升极片的压实密度，从而显著提高第二类电芯的能量密度，进而提高混合串联电池模组的能量密度；此外，也可以保证第一类电芯与第二类电芯的负极活性物质的平均粒径比较接近，这有利于保持极片的空间结构，同时抑制极片的反弹，在使用过程中保持稳定的孔隙率，有利于电芯循环寿命及循环膨胀力的改善。
79. 电芯数量
80.在本申请的一个或多个实施方式中，第一类电芯的数量N与第二类电芯的数量M的比值N/M可以大于等于1。在一可选实施方式中，第一类电芯的数量N与第二类电芯的数量M的比值N/M可以在大于等于1.5且小于等于200的范围内。在又一可选实施方式中，第一类电芯的数量N与第二类电芯的数量M的比值N/M可以在大于等于2且小于等于100的范围内。
81.举例而言，比值N/M可以是例如1.0、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100、105、110、115、120、125、130、135、140、145、150、155、160、165、170、175、180、185、190、195、200，等等。需要强调的是，虽然本申请将上述数值并列地列出，但是并不意味着发明人承认比值N/M在上述任意两个数值作为端点组成的数值范围内都可以得到相当或相近的性能。
82.上述第一类电芯和第二类电芯数量的匹配过程可以主要从能量密 度的差异、膨胀力增长的差异、动力学性能的差异、温升的差异、成本的差异、安全性能的差异等角度进行设计。在比值N/M的上述范围内，电池模组整体的性能较优。
83. 电芯排布方式
84.在本申请的一个或多个实施方式中，第一类电芯与第二类电芯可以被间隔排布。此外，在优选实施方式中，第一类电芯可以被排布在电池模组/电池包的外围、两端和/或中间。
85.本申请的电芯排布方式可以有效地降低电池模组内部的局部应力，提升电池模组的结构稳定性和安全性。
86.图1A示出了一种低能量密度的示例性电芯排布方式。在图1A所示的示例中，四个低能量密度的第一类电芯以四边形的形式进行排布。
87.图1B示出了一种高能量密度的示例性电芯排布方式。在图1B所示的示例中，引入了一个高能量密度的第二类电芯，且与图1A所示的示例类似，三个低能量密度的第一类电芯与一个高能量密度的第二类电芯以四边形的形式进行混合排布。由于引入了高能量密度的第二类电芯，因此相较于图1A中的示例，图1B中的示例提高了所获得的电池模组整体的能量密度。
88.图1C示出了一种高能量密度、低应力且高保温的示例性电芯排布方式。在图1C所示的示例中，三个低能量密度的第一类电芯与一个高能量密度的第二类电芯以三角形的形式进行混合排布，三个第一类电芯将该第二类电芯围在中心，从而使得所得到的电池模组能量密度较高、局部应力降低并且高低温性能较好。
89.图2A和图2B示出了根据本申请的实施方式的示例性混合串联电池模组的排布方式，其中电芯编号(例如图2A中的“11”)的第一个数字表示是第一类电芯还是第二类电芯，第二个数字表示序号，用作区分。图2A中示出了一组电池模组，且图2B中示出了六组电池模组。
90.如图2B所示，混合串联电池模组的第一类电芯和第二类电芯之间可以间隔一个或多个第一类电芯，例如可以间隔2个、3个、4个、n个第一类电芯。如图所示，电池模组的端部电芯可以是一个或多个第一类电芯、或者一 个或多个第二类电芯，也可以是一个第一类电芯、一个第二类电芯。第二类电芯的位置可以是在电池模组的端部，也可以是在其他位置，或者同时占据电池模组的端部和除所述端部以外的其他位置。
91. 实施例和对比例
92.以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。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。
93.表1和表2示出了本申请的9个实施例，并示出了3个对比例作为对照。表1可以显示出第一类电芯的第一负极极片的负极活性物质的层间距d1与第二类电芯的第二负极极片的负极活性物质的层间距d2的比值d1/d2对电池模组在反复充放电过程中的膨胀力的影响。本领域技术人员可以理解，由于两类电芯的化学体系差异，因此对电池模组的膨胀力增长的改善非常困难。表2可以显示出第一类电芯的第一负极极片的负极活性物质的平均粒径S1与第二类电芯的第二负极极片的负极活性物质的平均粒径S2的比值S1/S2对电池模组的容量保持率的影响。容量保持率与电芯的循环寿命相关联。同等条件下，容量保持率越高，电池模组中的电芯的循环寿命越长。
表1
Figure PCTCN2022070126-appb-000001
表2
Figure PCTCN2022070126-appb-000002
94. 电芯的制备
95.[电解质]
96.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。
97.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。
98.在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
99.在一些实施方式中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
100.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芯某些性能的添加剂，例如改善电芯过充性能的添加剂、改善电芯高温或低温性能的添加剂等。
101.[隔离膜]
102.在一些实施方式中，电芯中还包括隔离膜。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。
103.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。
104.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。
105.下面提供用于制备电芯的一个示例。
(1)正极浆料的制备
将表1中的各正极活性物质、点状和片状导电碳、粘结剂聚偏二氟乙烯(PVDF)按96.2:2.7:1.1重量比在N-甲基吡咯烷酮(简写为NMP)溶剂中充分搅拌混合，使其形成均匀的、粘度为3000mPa·s～25000mPa·s的稳定浆料，浆料静置24～48小时，不发生凝胶、分层或者沉降等现象。
(2)正极极片的制备
将上述制得的正极材料浆料以18mg/cm 2的涂布量均匀地涂覆于正极集流体Al箔上，干燥后把极片冷压到设计压密，分条备用，得到正极极片。
(3)电解液的制备
将等量体积的碳酸亚乙酯溶解在碳酸丙烯酯中，然后依照1mol/L的浓度将适量的六氟磷酸锂盐均匀溶解在该混合溶剂中备用，得到电解液。
(4)负极极片的制备
将负极活性材料例如石墨与导电炭、粘结剂聚苯乙烯丁二烯共聚物(SBR)、 增稠剂羧甲基纤维素钠(CMC)按96.6:0.8:1.8:0.8重量比在水溶剂中充分搅拌混合，使其形成均匀的负极稳定浆料；将此浆料以11mg/cm 2的涂布量均匀地涂覆于负极集流体Cu箔上，干燥后把极片冷压到设计压密，分条备用。
(5)隔离膜
选用聚乙烯(PE)或者聚丙烯(PP)等作为隔离膜，隔离膜表面根据需要可以有无机和/或有机涂层。
(6)电芯的制备
采用常规的电芯制作工艺，将正极极片、隔离膜和负极极片一起卷绕成裸电芯，然后置入电池壳体中，注入电解液，随之进行化成、密封等工序，最终得到可充电动力电芯。
106.在一些实施例中，电芯可以包括外包装，用于封装上述电极组件和电解质。在一些实施例中，电芯的外包装可以是软包，例如袋式软包。软包的材质可以是塑料，例如聚丙烯PP、聚对苯二甲酸丁二醇酯PBT、聚丁二酸丁二醇酯PBS等中的一种或几种。电芯的外包装也可以是硬壳，例如硬塑料壳、铝壳、钢壳等。
107.在一些实施例中，外包装可包括壳体和盖板。其中，壳体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。壳体具有与容纳腔连通的开口，盖板能够盖设于所述开口，以封闭所述容纳腔。
108.正极极片、负极极片和隔离膜可经叠片或卷绕形成叠片结构电极组件或卷绕结构电极组件。将该电极组件封装于所述容纳腔。电解质可采用电解液，电解液浸润于电极组件中。
109. 电池包的制备
110.在本申请的实施方式中，在将一个或多个上述第一类电芯和一个或多个上述第二类电芯组装成电池模组之后，可以将两个或更多个电池模组组装成电池包。电池包所含电池模组的数量取决于电池包的应用和单个电池模组的参数。电池包可以包括电池箱(如图3A-图3C所示)和设置于电池箱中的多个电池模组。电池箱包括上箱体和下箱体，上箱体可以盖在下箱体上并与之配合，形成用于容纳电池模组的封闭空间。两个或更多个电池模组可以按照所需 的方式排布于该电池箱中。在本申请中，“电池包”是由一个或多个电池模组(或者由多个电芯直接形成的组合)进一步装配电池管理系统、热管理系统等各种控制和保护系统而制成的(如图4A-图4C所示)。
111.应当注意的是，为了简化本申请的表述，从而帮助对一个或多个实施方式的理解，前文对本申请实施方式的描述中，有时会将多种特征归并至一个实施方式、附图或对其的描述中。但是，这种披露方法并不意味着本申请对象所需要的特征比权利要求中提及的特征多。实际上，实施方式的特征可以少于上述披露的单个实施方式的全部特征。
112.需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (13)

  1. 一种混合串联电池模组，其特征在于，所述混合串联电池模组包括：
    一个或多个第一类电芯，每一个所述第一类电芯包括第一负极极片；以及
    一个或多个第二类电芯，每一个所述第二类电芯包括第二负极极片；其中
    所述第一类电芯的能量密度小于所述第二类电芯的能量密度，以及
    所述第一负极极片的负极活性物质的层间距d1大于所述第二负极极片的负极活性物质的层间距d2，并且在0％荷电状态下，所述层间距d1与所述层间距d2的比值d1/d2在大于等于1.005且小于等于1.600的范围内。
  2. 根据权利要求1所述的混合串联电池模组，其特征在于，在0％荷电状态下，所述层间距d1与所述层间距d2的比值d1/d2在大于等于1.010且小于等于1.200的范围内，可选地，在0％荷电状态下，所述层间距d1与所述层间距d2的比值d1/d2在大于等于1.100且小于等于1.170的范围内。
  3. 根据权利要求1或2所述的混合串联电池模组，其特征在于，所述第一类电芯的能量密度与所述第二类电芯的能量密度相匹配使得所述第一类电芯的体积V1与所述第二类电芯的体积V2的比值V1/V2在大于0.20且小于等于20.00的范围内，可选地，在大于等于0.40且小于等于5.00的范围内，进一步可选地，在大于等于1.00且小于等于2.10的范围内。
  4. 根据权利要求1～3中任一项所述的混合串联电池模组，其特征在于，所述第一类电芯的能量密度与所述第二类电芯的能量密度相匹配使得所述第一类电芯的厚度T1与所述第二类电芯的厚度T2的比值T1/T2在大于1.00且小于等于20.00的范围内，可选地，在大于等于1.02且小于等于5.00的范围内，进一步可选地，在大于等于1.05且小于等于2.10的范围内。
  5. 根据权利要求1～4中任一项所述的混合串联电池模组，其特征在于， 所述第一类电芯的体积能量密度E1与所述第二类电芯的体积能量密度E2的比值E1/E2在大于等于0.20且小于等于1.00的范围内，可选地，所述第一类电芯的体积能量密度E1与所述第二类电芯的体积能量密度E2的比值E1/E2在大于等于0.25且小于等于0.90的范围内，进一步可选地，所述第一类电芯的体积能量密度E1与所述第二类电芯的体积能量密度E2的比值E1/E2在大于等于0.30且小于等于0.86的范围内。
  6. 根据权利要求1～5中任一项所述的混合串联电池模组，其特征在于，所述第一类电芯的重量能量密度G1与所述第二类电芯的重量能量密度G2的比值G1/G2在大于等于0.20且小于等于1.00的范围内，可选地，所述第一类电芯的重量能量密度G1与所述第二类电芯的重量能量密度G2的比值G1/G2在大于等于0.30且小于等于0.99的范围内，进一步可选地，所述第一类电芯的重量能量密度G1与所述第二类电芯的重量能量密度G2的比值G1/G2在大于等于0.40且小于等于0.95的范围内。
  7. 根据权利要求1～6中任一项所述的混合串联电池模组，其特征在于，在不包括基材的情况下，所述第一负极极片的孔隙率P1与所述第二负极极片的孔隙率P2的比值P1/P2在大于等于0.75且小于等于3.00的范围内，可选地，在不包括基材的情况下，所述第一负极极片的孔隙率P1与所述第二负极极片的孔隙率P2的比值P1/P2在大于等于0.80且小于等于2.00的范围内，进一步可选地，在不包括基材的情况下，所述第一负极极片的孔隙率P1与所述第二负极极片的孔隙率P2的比值P1/P2在大于等于0.90且小于等于1.50的范围内。
  8. 根据权利要求1～7中任一项所述的混合串联电池模组，其特征在于，所述第一负极极片的负极活性物质的平均粒径S1与所述第二负极极片的负极活性物质的平均粒径S2的比值S1/S2在大于等于0.10且小于1.00的范围内，可选地，所述第一负极极片的负极活性物质的平均粒径S1与所述第二负极极片的负极活性物质的平均粒径S2的比值S1/S2在大于等于0.15且小于等于 0.95的范围内，进一步可选地，所述第一负极极片的负极活性物质的平均粒径S1与所述第二负极极片的负极活性物质的平均粒径S2的比值S1/S2在大于等于0.30且小于等于0.90的范围内。
  9. 根据权利要求1～8中任一项所述的混合串联电池模组，其特征在于，所述第一类电芯的数量N与所述第二类电芯的数量M的比值N/M大于等于1，可选地，所述第一类电芯的数量N与所述第二类电芯的数量M的比值N/M在大于等于1.5且小于等于200的范围内，进一步可选地，所述第一类电芯的数量N与所述第二类电芯的数量M的比值N/M在大于等于2且小于等于100的范围内。
  10. 根据权利要求1～9中任一项所述的混合串联电池模组，其特征在于，所述第一类电芯与所述第二类电芯间隔排布。
  11. 根据权利要求1～10中任一项所述的混合串联电池模组，其特征在于，所述第一类电芯被排布在所述混合串联电池模组的两端和中间。
  12. 一种电池包，其特征在于，包括权利要求1～11中任一项所述的混合串联电池模组。
  13. 一种用电装置，其特征在于，包括权利要求1～11中任一项所述的混合串联电池模组或权利要求11所述的电池包中的至少一种。
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